Book of Abstracts

14th Nordic Symposium on Catalysis August 29-31, 2010 Marienlyst, Denmark

We thank a number of sponsors for helping to make this symposium possible:

The organizing committee:

Anker Degn Jensen (DTU Chemical Eng.) Jan-Dierk Grunwaldt (DTU Chemical Eng.) John Woodley (DTU Chemical Eng.) Anders Riisager (DTU Chemistry) Thomas Bligaard (DTU Physics) Sren Dahl (DTU Physics) Jane Hvolbk Nielsen (DTU Physics) Jeppe Vang Lauritsen (AU Physics) Bo Brummerstedt Iversen (AU Chemistry) Stig Helveg (Haldor Topse A/S) Claus Hviid Christensen (Haldor Topse A/S) Gurli Mogensen (IDA, K-gruppen)

The scientific programme consists of:

3 Plenary lectures 4 Nordic Keynote talks 48 Oral contributions 100 Poster presentations This booklet contains an abstract for each of these 155 scientific presentations. Posters numbered P1-P50 will be presented at the poster session in the evening on Sunday, August 29th, while posters with numbers P51P100 will be presented at the poster session after lunch on Monday, August 30th.

Program - 14th Nordic Symposium on Catalysis

Sunday, 29.08.2010
Time 10.00 12.00 13.30 13.30 13.40 Kronborgsalen Registration open Welcome and lunch Opening of the conference Marienlystsalen (Anker Degn Jensen) Session 1, Marienlystsalen, Session chair: Ib Chorkendorff P1: Catalytic strategies for the conversion of biomass-derived carbohydrates to liquid hydrocarbon fuels James A. Dumesic Department of Chemical and Biological Engineering, University of Wisconsin Madison Session 2, Marienlystsalen, Session chair: Anders Riisager Session 3, Kronborgsalen, Session chair: Lars Pettersson O8: Microstructured reactors in compact conversion of natural gas and O1: Conversion of Sugars into Methyl Lactate using biomass to liquid fuels and hydrogen Lewis acidic Zeotype Catalysts Hilde Venvik Martin Spangsberg Holm Centre for Catalysis and Sustainable Chemistry, Dept. Chemistry, Dept. Chemical Engineering, Tech. Univ. Denmark Norwegian University of Science and Technology (NTNU), Trondheim O2: Formic acid for vapour phase catalytic olefins hydrogenation O9: Application of microchannel reactors in the dehydrogenation of isobutane Dmitri A. Bulushev Reetta Karinen Chemical & Environmental Sciences Dept., University of Limerick Aalto University School of Science and Technology O3: Process considerations for the catalytic dehydration of sugars to 5O10: Photocatalytic measurements in -reactors hydroxymethylfurfural Peter C. K. Vesborg Jacob S. Jensen Center for Individual Nanoparticle Functionality, Tech. Univ. Denmark Dept. Chemical and Biochemical Engineering, Tech. Univ. Denmark Coffee break Session 4, Marienlystsalen, Session chair: Jan-Dierk Grunwaldt N1: Characterisation of Fishcer-Tropsch catalysts at realistic reaction conditions Magnus Rnning Dept. Chemical Engineering, Norwegian University of Science and Technology, Trondheim Session 5, Marienlystsalen, Session chair: Jan-Dierk Grunwaldt Session 6, Kronborgsalen, Session chair: Sren Dahl O4: Catalysts for sorbent enhanced reforming (SER) of methane O11: Direct Decomposition of NO on C-type Cubic Rare Earth Oxides in temperature swing reactors Kinetic Nobuhito Imanaka Christoph Sprung Dept. of Applied Chemistry, Osaka University Dept. Chemistry, University of Oslo O12: H2 activation of aromatic hydrocarbons over Ag/Al2O3 O5: Kinetics of steam reforming over ruthenium based catalysts diesel-SCR catalysts Tommy L. Jrgensen Hannes Kannisto Haldor Topse A/S, Lyngby Competence Centre for Catalysis, Chalmers University of Technology O6: Hydrogen generation from low-sulphur diesel over Rh-based metallic O13: H2-promoted NOx adsorption/desorption over Ag/Al2O3: Transient experiments and TPD study monolithic catalyst N.A. Sadokhina Xanthias Karatzas Dept. Chemical Engineering and Technology, KTH, Stockholm Zelinsky Institute of Organic Chemistry, Moscow Marienlystsalen

13.40 14.25

14.25 14.50

14.50 15.15

15.15 15.40 15.40 16.10

16.10 16.45

16.45 17.10

17.10 17.35

17.35 18.00

18.00 18.25

19.00 -

O7: Direct evidence of strong interaction between PtO nanoparticles and carbon nanofibers O14: Alkali resistant Fe-zeolite catalysts for SCR of NO with NH3 Ingvar Kvande Siva Sankar Reddy Putluru Dept. Chemical Engineering, Norwegian University of Science and Dept. Chemical Engineering, Tech. Univ. Denmark Technology, Trondheim, and SINTEF Materials and Chemistry, Trondheim Poster Session 1 with evening buffet

Monday, 30.08.2010
Time Marienlystsalen Kronborgsalen Session 6, Marienlystsalen, Session chair: Astrid Boisen P2: Biocatalysis: a curiosity or a real synthetic option? Wolfgang Kroutil Department of Chemistry, University of Graz Session 7A, Marienlystsalen, Session chair: Magali Boutonnet Session 8A, Kronborgsalen, Session chair: Jens Sehested O15: Novel catalyst on a basis of immobilized horseradish peroxidase for O26: Kinetics of selective oxidation of sugars over gold catalysts biology active substances synthesis Bright Kusema Valentine Doluda Process Chemistry Center, bo Akademi University Dept. of biotechnology and chemistry, Tver state technical university O16: High-Oleic Sunflower Oil as a One-Pot Reaction Feedstock for O27: Selective gold-catalysed aerobic oxidations under ambient conditions Dimethyl 1,19Nonadecanedioate Synthesis Sren Kegns Guido Walther Centre for Catalysis and Sustainable Chemistry, Dept. Chemistry, Leibniz Institute for Catalysis, Rostock Tech. Univ. Denmark Coffee break Session 9, Marienlystsalen, Session chair: Sren Dahl N2: Catalytic reduction of nitrogen oxides in lean exhausts from vehicles Louise Olsson Dept. Chemical and Biological Engineering, Chalmers University of Technology Session 7B, Marienlystsalen, Session chair: Magali Boutonnet Session 8B, Kronborgsalen, Session chair: Jens Sehested O17: Effect of biomass derived synthesis gas impurities on TOF and O28: Using TPD data in determination of ammonia hydrocarbon selectivity in cobalt Fischer-Tropsch synthesis sorption kinetics on HZSM-5 yvind Borg Sonja K. Kouva Statoil Research Center, Trondheim Aalto University School of Science and Technology O29: Structural environments for surface sites in boron- and phosphorousmodified alumina catalysts from single- and double-resonance 1H, 11B, 31P, O18: On the selectivity of cobalt-based Fischer-Tropsch catalysts and 27Al MAS NMR experiments Matteo Lualdi Jrgen Skibsted Chemical Technology, Royal Institute of Technology (KTH), Stockholm Instrument Centre for Solid-State NMR Spectroscopy, and Interdisciplinary Nanoscience Center (iNANO), Dept. Chemistry, Aarhus University Lunch followed by Poster Session 2 Session 10, Marienlystsalen, Session chair: Ingemar Oldenbrand Session 11, Kronborgsalen, Session chair: Jeppe Vang Lauritsen O19: In-situ & Operando spectroscopic methods for studying industrial O30: Advances in transmission electron microscopy for catalysis applications and deactivation phenomena of modified vanadium oxide catalysts for the NH3-SCR reaction Alfons M. Molenbroek Sren Birk Rasmussen Haldor Topse A/S, Lyngby Instituto de Catlisis y Petroleoqumica, Madrid O20: Catalytic conversion of syngas into mixed long-chain alcohols over cobalt-molybdenum sulfide Jakob Munkholt Christensen Department of Chemical and Biochemical Engineering, Technical University of Denmark O31: Environmental TEM of the Dynamics of Catalyst Particles Thomas W. Hansen Center for Electron Nanoscopy (CEN), Tech. Univ. Denmark

8.30 9.15

9.15 9.40

9.40 10.05 10.05 10.35

10.35 11.10

11.10 11.35

11.35 12.00

12.00 14.00

14.00 14.25

14.25 14.50

14.50 15.15

O21: Lean NOx reduction with various bio-diesels as reducing agents Sara Erkfeldt Volvo Technology Corporation, and Competence Centre for Catalysis, Chalmers University of Technology O22: Special characteristics of dimethyl ether as reducing agent in continuous lean NOx catalysis Stefanie Tamm Competence Centre for Catalysis, and Applied Surface Chemistry, Chalmers University of Technology Session 12, Marienlystsalen, Session chair: Gurli Mogensen

O32: Identical locations transmission electron microscopy study of Pt/C catalyst corrosion under oxygen reduction reaction conditions Francisco J. Prez-Alonso Center for Individual Nanoparticle Functionality, Dept. Physics, Tech. Univ. Denmark O33: Structural characterization of materials relevant to catalysis Lars F Lundegaard Haldor Topse A/S, Lyngby

15.15 15.40

15.40 16.10

Coffee break N3: Catalysis in VOC Abatement Satu Ojala Department of Process & Environmental Engineering, University of Oulu Session 13, Marienlystsalen, Session chair: Johannes Due-Hansen Session 14, Kronborgsalen, Session chair: Jane Hvolbk Nielsen O23: Epoxidation of Olefins Catalyzed by the Cobalt based Metal-Organic O34: In situ studies of Pd and Rh model catalysts Framework STA-12(Co) Edvin Lundgren Matthias J. Beier Division of Synchrotron Radiation Research, Lund University Dept. Chemical Engineering, Tech. Univ. Denmark, and ETH Zurich O24: Cobalt complexes with tripodal ligands in oxidation catalysis O35: Making EXAFS surface sensitive? Red-ox cycles on Rh/Al2O3 Susanne Mossin Davide Ferri Centre for Catalysis and Sustainable Chemistry, Dept. Chemistry, EMPA, Lab. for Solid State Chemistry and Catalysis, Dbendorf Tech. Univ. Denmark O36: High throughput experimentation as an efficient tool for the testing of O25: Oxidation of DCM and PCE laboratory vs. industrial scale study hydroprocessing catalysts Satu Pitkaho Philipp Hauck Dept. of Process and Environmental Engineering, Univ. of Oulu hte Aktiengesellschaft, Heidelberg Conference dinner and Berzelius Award Ceremony

16.10 16.45

16.45 17.10

17.10 17.35

17.35 18.00 18.30 -

Tuesday, 31.08.2010
Time Marienlystsalen Kronborgsalen Session 15, Marienlystsalen, Session chair: Thomas Bligaard P3: Surface-mediated oxygen-assisted reactions of amines and alcohols on single crystal surfaces of metallic silver and gold Robert J. Madix School of Engineering and Applied Sciences, Harvard University Session 16A, Marienlystsalen, Session chair: Thomas Bligaard Session 17A, Kronborgsalen, Session chair: Magnus Rnning O37: Probing the atomic-scale details of molecular adsorption on MoS2 and O43: Deactivation of ion exchange catalysts by acetonitrile and methylamine CoMoS nanoclusters in hydrotreating catalysis Carles Fit Jeppe V. Lauritsen Dept. Chemical Engineering, University of Barcelona Interdisciplinary Nanoscience Center (iNANO), Aarhus Univ. O44: Glycerol etherification to dimers using basic and acidic catalysts O38: Reactivity of ruthenium steps Andreas Martin Kenneth Nielsen Center for Individual Nanoparticle Functionality, Tech. Univ. Denmark Leibniz Institute for Catalysis, Rostock Coffee break Session 16B, Marienlystsalen, Session chair: Thomas Bligaard Session 17B, Kronborgsalen, Session chair: Magnus Rnning O45: In-situ FT-IR mechanistic investigations of the zeolite catalyzed O39: Catalytic reaction between O2, CO and NO over Rh model catalysts methylation of benzene with methanol: H-ZSM-5 vs H-beta. Johan Gustafson Stian Svelle Div. of Synch. Radiation Research, Lund University inGAP center of research based innovation/Dept. of Chemistry, University of Oslo, Norway O40: CO methanation over Ru-Al2O3 catalysts: effects of chloride doping on O46: Mercury Oxidation in Flue Gases reaction activity and selectivity Karin Madsen Galletti Camilla Haldor Topse A/S, Lyngby and Dept. Chemical Engineering, Tech. Univ. Denmark Dept. Materials Science and Chemical Engineering, Politecnico di Torino Lunch Session 18, Marienlystsalen, Session chair: Anders Holmen Session 19, Kronborgsalen, Session chair: Anker Degn Jensen O41: Influence of phosphorous aging on diesel oxidation catalysts O47: Coupling of Methane with Li/MgO-Catalysts Alexander Winkler Sebastian Arndt Empa, Internal Combustion Engines Laboratory, Duebendorf, Switzerland Inst. Chemie, Technische Universitt Berlin O48: Snapshots of the catalyst structure during the partial oxidation of O42: Alloys of platinum and early transition metals as oxygen reduction methane electrocatalysts Jan-Dierk Grunwaldt Ifan E.L. Stephens Dept. Chemical Engineering, Tech. Univ. Denmark and Institute for Chemical Center for Individual Nanoparticle Functionality, Tech. Univ. Denmark Technology and Polymer Chemistry (ITCP), Karlsruhe Session 20, Marienlystsalen, Session chair: Anders Holmen N4: Catalysis Informatics Thomas Bligaard Center for Atomic-scale Materials Design, Tech. Univ. Denmark Presentation of NSC-2012 (Kalle Arve) / Closing Session & Poster Award Ceremony (Anker Degn Jensen)

9.00 9.45

9.45 10.10

10.10 10.35 10.35 11.10

11.10 11.35

11.35 12.00 12.00 13.30

13.30 13.55

13.55 14.20

14.20 14.45 14.45 15:00

Poster Session 1 (Sunday evening)

P1: Co catalysed Fischer-Tropsch synthesis in biofuel production Henrik Romar Kokkola University Consortium Chydenius, Finland P2: ZnO supported on Al2O3, SiO2, TiO2 and ZrO2 for the Activation of Methane, Ethane and Propane Sebastian Arndt Technische Universitt Berlin P3: The role of monomeric iron during the selective catalytic reduction of NOx by NH3 over Fe-BEA zeolite catalysts Martin Hj1,2 1 Haldor Topse A/S, 2DTU Chemical Engineering, Technical University of Denmark P4: The production of motor fuel and chemical compounds from the products of thermal processing of oil shales A.L.Lapidus N.D.Zelinsky Institute of Organic Chemistry RAS, Moscow P5: Gasification of oil-shales for hydrogen containing gas production A. Lapidus Gubkin Russian State University of Oil and Gas, Moscow P6: Molten salts stabilised palladium nanoparticles phosphine-free catalyst for the carbonylation of olefins, alcohols and benzyl halides O.L. Eliseev N.D. Zelinsky Institute of organic Chemistry RAS, Moscow P7: Chemoenzymatic combination of oxidase enzymes with titanium silicalite-1 Peter N. R. Vennestrm1,2 1 Haldor Topse A/S, 2 Dept. Chemical and Biochemical Engineering, Technical University of Denmark P8: Nitrogen tolerant hydrodesulfurization catalysts based on Rh and Ru promoted Mo/Al2O3 Z. Vt ICPF of the ASCR, Prague, Czech Republic P9: Catalytic Performance of Mixed-addenda Heteropolyanions as Inorganic Solid Catalysts in Lactonization of Various Diols Ali Gharib1,2 1 Department of Chemistry, Islamic Azad University, 2 Agricultural researches and services Center, Mashhad, IRAN P10: Catalytic Performance of Preyssler Heteropolyanions as HomogeneousCatalysts in Phenacetin(antiinflammatory) of p-Aminophenol Ali Gharib1,2 1 Department of Chemistry, Islamic Azad University, 2 Agricultural researches and services Center, Mashhad, IRAN P11: Catalytic Synthesis of 2,5-Disubstituted Oxazoles Using Preyssler Homogeneous Heteropolyacid Catalysts Ali Gharib1,2 1 Department of Chemistry, Islamic Azad University, 2 Agricultural researches and services Center, Mashhad, IRAN P12: Thermal ageing behavior of Pt-only TWC converters under simulated exhaust conditions: Effect of rare earths (CeO2, La2O3) and alkali (Na) modifiers M. Konsolakis Laboratory of Physical Chemistry and Chemical Processes, Department of Sciences, Technical University of Crete P13: Operando XANES for structure activity studies: Combustion of methane on Pd/Al2O3 under genuine conditions M. Santhosh Kumar

Empa, Lab. for Solid State Chemistry and Catalysis, Dbendorf, Switzerland P14: Dry reforming of methane with carbon dioxide over Ni/MgO-ZrO2 catalysts D.A. Bulushev CPI, CES, University of Limerick, Limerick, Ireland, P15: Characterization and catalytic activity of new metal-organic frameworks resulted from self-assembly of Ph3SnCl, K[Cu(CN)2] and nitrogen donor ligands Abeer S. Elsherbiny Chemistry Department, Faculty of Science, Tanta University, Egypt P16: Effect of cobalt particle size on Fischer-Tropsch hydrocarbon selectivities for -alumina as support Shreyas Rane Department of Chemical Engineering, NTNU, Trondheim, Norway P17: Solar Hydrogen Production by Photo-oxidation of Water From Iron Oxide Photoanodes Alan Kleiman Shwarsctein Catalysis for Sustainable Energy Center, Danish Technical University, DK-2800 Lyngby, Denmark P18: Characterization of the supported vanadium oxide catalysts by multispectroscopical approach Michal Setnika Dept. of Physical Chemistry, University of Pardubice P19: Pechini route in pore: Synthesis of supported catalysts by impregnation and calcination of roomtemperature polymerizable metal-complexes Tiejun Zhao Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim, Norway P20: The role of alpha-sites of a Fe-ZSM-5 catalyst in selective catalytic reduction of NOx by ammonia Dmitry E. Doronkin Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia P21: Hydroisomerization of Fischer-Tropsch wax on Pt/AlSBA-15 and Pt/SAPO-11 catalysts Gyrgy Plczmann Department of Hydrocarbon and Coal Processing, University of Pannonia P22: 95Mo MAS NMR of MoS2 Reveals Precise 95Mo Anisotropic Parameters from the Central and Satellite Transitions for Characterizing Its Structure Hans J. Jakobsen Instrument Centre for Solid-State NMR Spectroscopy, Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Denmark P23: Hydrogen Produced by Ru/(CuAg)xIn2xZn2(1-2x)S2 Photocatalysts via Water-Splitting Reaction Ien-Whei Chen Dept. Chemical Engineering, Tatung University, Taipei, Taiwan, R. O. C. P24: Characterization of the active sites in spent and regenerated ZSM-5 catalysts by 1H, 13C, 27Al, and 29Si MAS NMR spectroscopy Sren Srensen Instrument Centre for Solid-State NMR Spectroscopy and Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, Denmark. P25: Microwave irradiated Pd/Al2O3 catalysts for N2O decomposition Siva Sankar Reddy Putluru Department of Chemical Engineering, Technical University of Denmark, Denmark

P26: Investigation of the effect of oxygenic compounds on the isomerization of bioparaffins over Pt/SAPO-11 catalyst J. Hancsk Department of MOL Hydrocarbon and Coal Processing, Pannon University, Hungary P27: The effect of sulphur and water treatments on the performance of Pd/-zeolite diesel oxidation catalysts Mika Huuhtanen Dept. Process and Environmental Eng., University of Oulu, Finland P28: TiO2 on aligned CNF substrates for photocatalytic water splitting Asmira Delic Department of Chemical Engineering, NTNU, Trondheim, Norway P29: Improvement of photoelectrochemical hydrogen generation at p-type silicon by surface modification with noble metal free catalyst Yidong Hou Center for Individual Nanoparticle Functionality (CINF), Department of Physics, Technical University of Denmark P30: Electrochemical Fixation of Carbon Dioxide Wei Tang Center for Individual Nanoparticle Functionality, Department of Physics, Technical University of Denmark P31: Methane Oxidation on Gold A combined Microreactor and DFT Study Guido Walther Leibniz Institute for Catalysis, Rostock, Germany P32: Production of biocomponent containing gas oil with the coprocessing of vegetable oil-gas oil mixture Jen Hancsk Department of MOL Hydrocarbon and Coal Processing, University of Pannonia, Hungary P33: Hydrogenation of the aromatics and olefinic hydrocarbons of the FCC gasoline in the condition of deep desulphurisation G. Marsi University of Pannonia, MOL Department of Hydrocarbon and Coal Processing, Hungary P34: Titanium dioxide coating on polyurethane surfaces Ritva Lenkkeri Univ. of Oulu, Dept. of Proc. and Env. Eng., University of Oulu P35: Co-based Fischer-Tropsch Synthesis: an Operando study from catalyst activation to deactivation. Nikolaos E. Tsakoumis Department of Chemical Engineering, NTNU, Trondheim, Norway P36: Photocatalytic hydrogen production from a gas phase of water and ethanol Fabio Dionigi CINF, Department of Physics, Tech. Univ. Denmark P37: The role of Ni and Mo species in the hydrodeoxygenation of rapeseed oil on NiMo-alumina catalysts Peter Priecel University of Pardubice, Czech Republic P38: Surface and catalytic behavior of Potassium promoted Pd/Al2O3 catalysts during N2O reduction by alkanes or alkenes M. Konsolakis Department of Sciences, Technical University of Crete, Greece P39: Structure of Ni-based catalysts active in the oxidative dehydration of ethane and propane Lucie Smolkov

University of Pardubice, Czech Republic P40: Size-selective aerobic oxidation by highly stable gold nanoparticles embedded in zeolite crystals A.B. Laursen Haldor Topse A/S and DTU Chemical Engineering, DTU P41: Effective Cl-VOC removal from air on low-loaded (Au+Rh)/TiO2 catalysts A.V. Kucherov Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia P42: Peculiarities of VOC, S-VOC, and Cl-VOC removal from exhaust gases over oxidation catalysts of different types A.V. Kucherov Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia P43: Origin of in-situ reduction and oxidation of Co/Al2O3 in the Fischer-Tropsch Synthesis Jia Yang Department of Chemical Engineering, Norwegian University of Science & Technology, Trondheim, Norway P44: The SET Model for Catalysis Ragnar Larsson Chemical Engineering II, Chemical Center, University of Lund, Sweden P45: Selective Growth of SWNTs from CuOx-FeOx Catalyst Maoshuai He Department of Biotechnology and Chemical Technology, Aalto University, Finland P46: Selective catalytic reduction of NO with ethanol over carbon nanotube supported catalysts Anna Avila Dept. of Process and Environmental Eng., University of Oulu, Finland P47: Novel CNT-based catalyst materials for low temperature NH3-SCR of NO Anna Avila Dept. of Process and Environmental Eng., University of Oulu, Finland P48: The study of modified activated carbon characteristics by adsorption methods Hoang Kim Bong Moscow State Academy of Fine Chemical Technology P49: Influence of thermal pretreatment on the catalytic performance of Pd-Sb/TiO2 catalysts for acetoxylation of toluene N. Madaan Leibniz Institute for Catalysis at University of Rostock, Rostock, Germany P50: Monsanto carbonylation by Supported Ionic Liquid Phase (SILP) catalysis Christopher W. Hanning Centre for Catalysis and Sustainable Chemistry, DTU Chemistry, Denmark

Poster Session 2 (Monday noon):

P51: Rhodium-based catalysts promoted by Lithium on Si/Zr mesoporous oxides applied in syngas to ethanol conversion Luis Lpez Royal Institute Of Technology KTH, Stockholm Sweden and Instituto de Investigaciones Qumicas UMSA, La Paz Bolivia. P52: Density functional study on ethylene decomposition on flat and stepped Palladium J. Andersin Department of Chemistry, University of Jyvskyl, Finland P53: Ce-Zr based catalysts in CWAO process L. Rahikka University of Oulu, Department of Chemistry, and Kokkola University Consortium Chydenius, Finland P54: Catalytic wet air oxidation and photocatalysis in the removal of ethanol from wastewaters L. Rahikka University of Oulu, Department of Chemistry, and Kokkola University Consortium Chydenius, Finland P55: Effect of Pt nanoparticle size in the deep oxidation of C1-C6 n-alkane A.M. Gololobov Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia P56: TEM and SEM characterization and catalytic performance of Pd-Zn/C catalyst for selective acetylene hydrogenation prepared using Pd-Zn(OAc)4(OH2) complex I.S. Mashkovsky N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia P57: Sub-nanometer Pt films on top of Pt bimetallic alloys as new oxygen reduction electrocatalysts Tobias P. Johansson CINF, Institute of Physics, Technical University of Denmark P58: High-Output Catalyst Development in Energy Research Michael Schneider Chemspeed Technologies, Switzerland P59: The oxidation and CO reduction of Pd nano particles: A high pressure x-ray photoelectron spectroscopy study S. Blomberg Division of Synchrotron Radiation Research, Lund University, Sweden. P60: Optimizing feed concentrations for lean NOx reduction by HC-SCR over doped AG/AL2O3 Fredrik Gunnarsson Competence Centre for Catalysis, Department of Chemical and Biological Engineering, Chalmers University of Technology, Sweden P61: Simultaneous production of ethanol based fuel ethers and their corresponding alcohols Kurkijrvi Antti Faculty of Chemistry and Materials Sciences, Aalto University P62: New catalysts for dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids Tim Sthlberg Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark P63: Comparison of the Catalytic Activity of Supported Gold Nanoparticles on Ti-oxide and Ti-(oxy)-fluoride A. Alshammari Leibniz Institute for Catalysis, University of Rostock, Germany

P64: Catalytic oxidation of wastewaters under mild conditions A. Heponiemi University of Oulu, Department of Chemistry, University of Oulu P65: In situ DRIFTS investigation of methanol interaction with zirconia-supported noble metal catalysts Sanna Airaksinen Aalto University School of Science and Technology, Finland P66: Catalytic conversion of mono- and di-saccharides into ethyl levulinate with Brnsted acid ionic liquids Shunmugavel Saravanamurugan Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark P67: Valorisation of cellulose over metal modified mesoporous materials Mats Kldstrm Lab. of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, bo Akademi University, Finland P68: Trends of Fischer-Tropsch Synthesis at Transition metal surfaces Shengguang Wang Center for Atomic-scale Materials Design, Dept. Physics, Technical University of Denmark P69: Renewable building block for plastic industry: Gold-catalyzed oxidation of HMF to FDA in water Yury Y. Gorbanev Centre for Catalysis and Sustainable Chemistry, Technical University of Denmark P70: Imine formation by benign oxidative coupling of alcohols and amines using supported gold nanoparticles as catalyst Jerrik Mielby Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark P71: Photocatalytic liquid phase degradation of ethanol over titanium dioxide catalysts Minna Piril Univ. of Oulu, Dep. of Process and Env. Eng., University of Oulu P72: Functionalization of fatty acids in ionic liquids Mathilde Grau Srensen Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark P73: Application of ionic liquid catalysts in the production of biodiesel Helle Sndergaard Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark P74: NOx Selective Catalytic Reduction with Hydrocarbons and Hydrogen Effect Over Supported Metallic Catalysts Roberto Lanza KTH -Department of Chemical Engineering and Technology, Stockholm, Sweden P75: Oxidative dehydrogenation of ethane at short contact times Paul B. Radstake Department of Chemical Engineering, NTNU, Trondheim, Norway P76: The activating role of H2 on NO oxidation over Ag-Al2O3 Muhammad M. Azis Department of Chemical and Biological Engineering, Chalmers University of Technology, Sweden P77: Different approaches for the evaluation of reaction mechanisms in microkinetic modeling of methane partial oxidation M. Surma Dept. of Chemical Engineering, NTNU Trondheim, Norway

P78: Oxidation with environmentally benign heterogeneous metal catalysts Ester Eyjolfsdottir Centre for Catalysis and Sustainable Chemistry, Dept. of Chemistry, Technical University of Denmark P79: Effect of by-product CO on the hydrodeoxygenation of methyl esters Tuula-Riitta Viljava Aalto University, School of Science and Technology, Aalto P80: Hydrocracking of Fischer-Tropsch waxes over noble metal catalysts supported on amorphous silica-alumina Francesco Regali Department of Chemical Technology, KTH,Stockholm, Sweden P81: Selective Oxidation of Alcohols using Gold/Palladium Bioinorganic Catalysts M. Merroun Institut fr Radiochemie, Forschungszentrum Dresden Rossendorf, Germany. P82: Composite of Conducting Polymers, semiconducting oxides and Aligned CNT for Energy Storage Fan Huang Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim P83: Higher alcohol synthesis from syngas over Molybdenum based catalysts Robert Andersson KTH (Royal Institute of Technology), Chemical Technology, Stockholm, Sweden P84: Development of nanostructured electrodes on foils Estelle Vanhaecke Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim P85: Production of biomass derived synthesis gas by catalytic steam reforming Espen Standal Wangen Dept. Chemical Engineering, Norwegian University of Science and Technology, Trondheim P86: In situ deactivation study of the rhenium behaviour in Co-Re Fischer-Tropsch catalysts Alexey Voronov Department of Chemical Engineering, NTNU, Trondheim, Norway P87: Conversion of oxygenates over zeolite H-ZSM-5: Towards direct production of hydrocarbon fuels from biomass Uffe V. Mentzel Centre for Catalysis and Sustainable Chemistry, Technical University of Denmark and Haldor Topse A/S P88: The effect of hydrothermal aging on the structure and activity of three-way catalysts Davide Ferri Empa, Lab. for Solid State Chemistry and Catalysis, Dbendorf, Switzerland P89: Reaction mechanism of Ru based catalysts on methane partial oxidation Roberto Lanza KTH -Department of Chemical Engineering and Technology, Stockholm, Sweden P90: Structure sensitivity of NO, N2 and O2 dissociation over low-indexed transition-metal alloy surfaces Wei Guo Center for Atomic-scale Materials Design, Dept. of Physics, Technical University of Denmark P91: Scaling relations for intermediates for ammonia synthesis on nanoparticles Jakob G. Howalt Center for Atomic-scale Materials Design, Technical University of Denmark

P92: Structure-activity relationships of Pt/Al2O3-based diesel oxidation catalysts Alexey Boubnov Haldor Topse A/S and Nano Science Center, University of Copenhagen, Denmark P93: Heterogeneously Catalyzed Selective Hydrogenation Reactions In Supercritical Carbon Dioxide Nikolai E. Musko Chemical Engineering Department, Technical University of Denmark P94: Oxidation of 5-hydroxymethylfurfural with homogeneous Cu(I) catalysts Thomas S. Hansen Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark P95: Towards a generally applicable density functional including van der Waals interactions Jess Wellendorff CAMD, Department of Physics, Technical University of Denmark P96: Interrelation between Fe3+ and Cu2+ cations in the Cu-Fe-Beta catalyst for selective catalytic reduction of NOx by ammonia as evidenced by ESR Alexey V. Kucherov Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia P97: A study of the catalytic activity of ZrO2 in bio-oil production under near-critical water conditions D. F. Aarup Dept. of Chemistry and iNANO, Aarhus University, Denmark P98: Electrocatalysis on model surfaces: Overlayers, near-surface alloys and surface alloys of Cu-Pt Lone Bech CINF, Department of Physics, Technical University of Denmark P99: New Mesoporous Silica Supported Nickel Catalysts for Biomass Conversion Steven Fiddy Hiden Analytical Ltd, Warrington, UK P100: Reactivity of Heterogeneous Catalyst by DFT and Parameterized-Model Studies: Towards S tolerant Bimetallic Structures Nilay Inoglu Department of Chemical Engineering, Carnegie Mellon University, USA

Plenary 1 Catalytic strategies for the conversion of biomass-derived carbohydrates to liquid hydrocarbon fuels
James A. Dumesic Department of Chemical and Biological Engineering University of Wisconsin Madison E-mail: dumesic@engr.wisc.edu We outline how heterogeneous catalysts can be used in a cascade mode, where the effluent from the first reactor is fed to the second reactor, to selectively remove oxygen moieties from carbohydrates to produce specific classes of hydrocarbons for use as liquid transportation fuels. In one approach, a bimetallic catalyst in the first reactor is used to produce mono-functional compounds (such as alcohols, ketones, carboxylic acids, and heterocycles), and acidic zeolite catalysts or bi-functional catalysts containing metal and acid/base sites in a second reactor are used to achieve C-C coupling reactions. We discuss how the activity and selectivity of the catalyst in the first reactor can be controlled by the composition of the catalyst and the reaction conditions, and we show how the extent of C-C coupling in the second reactor can be controlled by combining ketonization reactions with aldol-condensation processes over various combinations of mixed-oxide catalysts. We will also present results for a cascade catalytic process for the deconstruction of cellulose in an aqueous solution of sulfuric acid to produce -valerolactone (GVL) that can subsequently be converted catalytically with high yields to nonenes or butenes. These alkene products are hydrophobic and separate spontaneously from water, yet can be processed further to liquid fuel components for gasoline, jet and Diesel fuels by a combination of acid-catalyzed isomerization, oligomerization, and cracking, followed optionally by hydrogenation to form alkanes.

Plenary 2 Biocatalysis: a curiosity or a real synthetic option?

W. Kroutil, D. Koszeleski, F. Mutti, K. Tauber, J. Schrittwieser, V. Resch, E. Siirola University of Graz, Department of Chemistry, Heinrichstrasse 28, 18010 Graz, Austria E-mail: wolfgang.kroutil@uni-graz.at Although lipases can be considered as broadly accepted biocatalysts for organic synthesis (e.g. for kinetic resolution or dynamic resolution), other enzyme classes are not yet so frequently applied in organic synthetic labs. We will show that various redox enzymes can efficiently be employed for the preparation of (a) optical pure sec-alcohols via asymmetric reduction of the corresponding ketone or deracemisation of racalcohols, (b) optical pure -chiral primary amines via formal asymmetric reductive amination of ketones and (c) optical pure scoulerine derivatives via enantioselective C-C bond formation. The asymmetric reduction of ketones was performed by alcohol dehydrogenases via hydrogen transfer employing 2-propanol as formal reducing agent, thus hydride donor [1]; sec-alcohol could be deracemised by coupling the asymmetric reduction with an enantioselective concurrent oxidation step leading finally to optically pure alcohols with up to >99% e.e. and conversion, whereby the oxidation and reduction were performed simultaneously in one pot without compartmentalisation [2]. -Chiral primary amines were obtained by employing -transaminases either starting from prochiral ketones [3] or deracemisation of rac-amines [4]. (S)-Scoulerine derivatives were obtained by transformation of reticuline derivatives via enantioselective intra-molecular alkylation of phenol employing an enzyme named berberine bridge enzyme originating from California poppy. REFERENCES [1] K. Edegger, C. C. Gruber, T. M. Poessl, S. R. Wallner, I. Lavandera, K. Faber, F. Niehaus, J. Eck, R. Oehrlein, A. Hafner, W. Kroutil, Chem. Commun. 2006, 2402-2404. [2] (a) C. V. Voss, C. C. Gruber, W. Kroutil, Angew. Chem. Int. Ed. 2008, 47, 741-745. (b) C. V. Voss, C. C. Gruber, K. Faber, T. Knaus, P. Macheroux, W. Kroutil, J. Am. Chem. Soc. 2008, 130, 13969 13972. [3] (a) D. Koszelewski, I. Lavandera, D. Clay, G. M. Guebitz, D. Rozzell, W. Kroutil, Angew. Chem. Int. Ed. 2008, 47, 9337-9340. (b) D. Koszelewski, M. Gritzer, D. Clay, B. Seisser, W. Kroutil, ChemCatChem 2010, 2, 73-77. [4] D. Koszelewski, D. Pressnitz, D. Clay, W. Kroutil, Org. Lett. 2009, 11, 4810-4812.

Plenary 3 Surface-mediated oxygen-assisted reactions of amines and alcohols on single crystal surfaces of metallic silver and gold
Robert J. Madix School of Engineering and Applied Sciences Harvard University E-mail: rmadix@seas.harvard.edu The oxygen-assisted catalytic coupling of alcohols with both other alcohols and amines over metallic gold has been observed in the solution phase in several laboratories. In some cases this reaction can be understood in terms of successive surface and solution phase reactions. Evidence will be presented to show that these reactions also occur entirely on the surfaces of metallic gold or silver without the necessity of reactions in the ambient phase. In general these reactions involve activation of the amine to form adsorbed amides and of the alcohol to form adsorbed alkoxides by adsorbed atomic oxygen, which acts as a strong Brnsted base,. These adsorbed intermediates then react nucleophilically with adsorbed alkoxides to form hemiaminals or hemiacetals, respectively, which then yield the coupled products by H elimination. Though the mechanistic features are similar on gold and silver surfaces, there are intrinsic differences in the reactions. On gold product formation is rate-limited by desorption of the product, whereas on silver, -H elimination is rate-determining. The formation of the hemiaminal or hemiacetal appears to occur well below room temperature on gold, suggesting facile reaction of the amide intermediate with the alkoxide (or adsorbed aldehyde). In addition, the mechanistic concepts can be extended to understand other recently reported reactions of amines in solution over metallic gold.

NK 1 Characterisation of Fishcer-Tropsch catalysts at realistic reaction conditions

Magnus Rnning Department of Chemical Engineering, Norwegian University of Science and Technology (NTNU) NO-7491 Trondheim, Norway E-mail: ronning@chemeng.ntnu.no Cobalt is considered to be the most favourable element for the synthesis of long-chain hydrocarbons from natural gas [1]. It is known that addition of a noble metal such as rhenium mainly enhances catalysts reducibility and increases dispersion [2]. However, catalyst deactivation is a persistent challenge in the Fischer-Tropsch synthesis [3]. In situ characterisation techniques that are capable of providing information about the catalyst under realistic working conditions are necessary and essentially the only way to obtain accurate information about the active phase of the catalyst at industrially relevant conditions. Realistic FT conditions imply temperatures in the range 473-523 K and a pressure well above ambient. Furthermore, the feed conveniently can be concentrated syngas with H2/CO at the usage ratio of 2.1. The conversion level should be high (~50%) with a corresponding high selectivity towards C5+ hydrocarbons. The characterisation techniques need to be able to operate at these conditions. In addition, they should be able to distinguish the active phase from the support and from the produced wax. In the present study rhenium promoted cobalt catalysts supported on -Al2O3 have been characterised in a combined in situ XRD-XAS set-up at realistic Fischer-Tropsch conditions (483K, 18 bar). The behaviour of a laboratory plug flow reactor can be simulated in the cell and the conversion level can be monitored using an on-line MS. A gas feeding system dedicated for in situ studies in a controlled environment has been installed at the Swiss-Norwegian Beamlines (SNBL) at the ESRF. The system is especially designed for in situ XAS and XRD studies of catalysts. The system is designed to be able to operate at pressures up to 20 bars using a wide range of reaction gases [3]. The X-ray techniques were applied in order to detect structural changes in the catalyst during initial stages of the FT synthesis. The results from the in situ measurements are supplemented by results from other techniques such as Raman, TGA-DTA, transient kinetics and also kinetic measurements from laboratory plug flow reactors. References [1] M.E. Dry Catalysis Today 71 (2002) 227 [2] . Borg, N. Hammer, S. Eri, O.A. Lindvg, R. Myrstad, E.A. Blekkan, M. Rnning, E. Rytter, A. Holmen, Catalysis Today 142 (2009) 70 [3] N.E. Tsakoumis, M. Rnning, . Borg, E. Rytter, A. Holmen, Catal. Today (2010), doi:10.1016/j.cattod.2010.02.077 [4] M. Rnning, N.E. Tsakoumis, A. Voronov, R.E. Johnsen, P. Norby, W. van Beek, . Borg, E. Rytter, A. Holmen, Catal. Today; doi:10.1016/j.cattod.2009.10.010

NK 2 Catalytic reduction of nitrogen oxides in lean exhausts from vehicles

Louise Olsson Competence Centre for Catalysis, Chemical Engineering, Chalmers University of Technology, Sweden E-mail: louise.olsson@chalmers.se This presentation will focus on results from experiments and kinetic modelling of NOx reduction from lean exhausts (oxygen excess). Lean exhausts are present after diesel and lean burn gasoline engines. A standard three way catalyst (TWC) is not able to reduce the NOx due to that the noble metal sites will be covered by oxygen. There are different concepts for solving this, where NOx storage and selective catalytic reduction (SCR) are two important technologies. In NOx storage the gas is altered between long lean periods (minutes) and short rich pulses (seconds). During lean conditions NOx is stored on the catalyst forming barium nitrates and during the rich pulses the nitrates decomposes and the NOx is reduced on the noble metal sites. For the concept urea SCR is urea injected before the catalyst. The urea decomposes and forms ammonia which reacts selectively with the NOx over the catalyst. In this presentation results from NOx storage, ammonia SCR and also diesel oxidation catalysts (DOC) will be shown. NOx storage catalysts are deactivated when exposed to sulphur and this is investigated in detail using both experiments and kinetic modelling [1]. The NOx storage was found to decrease during SO2 exposure, and the decrease was linear and dose dependent. In addition, we investigated different regeneration strategies. When using 500 ppm H2 for 60min at 700C the regeneration was poor. However, when adding 5% CO2 to the 500 ppm H2 the regeneration was increased drastically. A kinetic model was developed, containing three sub-models: (i) NOx storage and regeneration, (ii) oxygen storage and reduction and (iii) sulfur poisoning and sulfur regeneration. Ammonia SCR have been investigated in detail [2-4]. A newly developed methodology for determining the coverage dependent activation energy with independent experiments will be demonstrated [5]. This is done by conducting an ammonia stepwise experiment, using a combined micro calorimeter and FTIR. This resulted in the coverage dependent heat of adsorption of ammonia on CuBeta. Further, experimental results from hydro carbon poisoning of the individual steps in NH3 SCR will be shown [6]. In more detail we investigated the effect of propene and n-octane on ammonia storage, ammonia oxidation, standard SCR and rapid SCR, with varying HC concentration. Further, NO oxidation over the DOC is important, since NO2 will increase the regeneration rate of the particlulate filter and also 50% NO2 in the NOx increases the SCR reaction significantly [7]. Results from improving NO oxidation using sulphur pretreatments will be shown. References [1] L. Olsson, M. Fredriksson, R.J. Blint, Submitted. (2010). [2] H. Sjvall, R.J. Blint, A. Gopinath, L. Olsson, Ind. & Eng. Chem. Res. 49 (2010) 39. [3] L. Olsson, H. Sjovall, R.J. Blint, Applied Catalysis B-Environmental 81 (2008) 203-217. [4] H. Sjvall, R.J. Blint, L. Olsson, Appl. Catal. B 92 (2009) 138. [5] N. Wilken, K. Kamasamudram, N.W. Currier, J. Li, A. Yezerets, L. Olsson, Catalysis Today 151 (2010) 237. [6] H. Sjovall, L. Olsson, Submitted. (2010). [7] L. Olsson, H. Karlsson, Catalysis Today 147S (2009) S290.

NK 3 Catalysis in VOC Abatement

1

Satu Ojala1, Satu Pitkaho1, Tiina Laitinen1, Niina Niskala1 and Riitta L. Keiski1 Dept. of Process & Env. Eng., MHTP lab., POB 4300, FIN-90014 University of Oulu E-mail: satu.ojala@oulu.fi

Catalytic abatement of volatile organic compounds (VOCs) is efficient, cost-effective and environmentally sound way to treat these harmful emissions. However, the process is not straightforward due to a large variety of different VOCs. One can imagine the magnitude of the group of different VOCs when one realizes that not only normal volatile hydrocarbons are included, but also the compounds including oxygen, chlorine, sulphur etc. Any hydrocarbon that is volatile at room temperature or particular conditions of the usage can be included to VOCs. Due to the variety of compounds, also the environmental and health effects are varied. In general, it is estimated that the greenhouse-effect of NMVOCs is 11 times higher than that of CO2. Similarly, depending on the composition and concentration of the VOC emission mixtures, the abatement technology should be optimized. The catalysts used in total oxidation of VOCs contain generally noble metals supported on metal oxides. Typically used Pt has proven to be a highly active and stabile catalyst. However, in the case of sulphurcontaining VOCs, Pt is too active, and causes finally formation of H2SO4 that causes problems with materials of construction. Quite recently, Au has been tested in S-VOC oxidation where it has been observed to be resistant to poisoning and more selective towards desired oxidation products (SO2, CO2 and H2O) than Pt. In the case of Cl-VOCs especially vanadium-oxide containing catalysts have shown to be not only selective towards HCl, CO2 and H2O formation, but also very active. Shifting from noble-metal based catalysts towards cheaper metal oxide catalysts can also be seen in the field of VOC catalysis. Several materials containing mixed oxides, perovskites, zeolites, hydrotalcitematerials etc has been developed and tested in total oxidation of VOCs. The usage of metal oxides in special cases where partial oxidation can be used to reduce VOC emissions have also been studied. For example partial oxidation of pulp mill TRS emissions, that contain methanol and mercaptans to formaldehyde, can be done with V2O5-containing catalysts. The shifting from destruction-based methods towards production-based methods is also industrially interesting, since it may have significant economic benefits. In addition to catalyst development, also development of novel process technologies and accurate emission measurement technologies with low detection limits are important. Autothermal reverse flow reactors have been already used for over ten years in industrial VOC abatement. Novel, interesting catalytic VOC abatement technologies include for example microwave-based and photocatalytic processes. Recently, efforts towards combining water treatment and following VOC abatement have been started. Hybrid processes are also planned to improve gas abatement (e.g. washing of product HCl), but also possible utilization of formed CO2 has been considered. Continuous, qualitative and quantitative measurements to verify the abatement efficiencies are under development, including for example FTIR/PAS technology. All these new efforts done during the recent years are directing towards development of more sustainable processes.

NK 4 Catalysis Informatics
Thomas Bligaard Center for Atomic-scale Materials Design Department of Physics, Technical University of Denmark E-mail: bligaard@fysik.dtu.dk Electronic structure methods based on density functional theory have reached a level of speed and accuracy where they can be used to describe complete catalytic reactions on transition metal surfaces. Simulations now complement experiments to give unprecedented insight into surface processes, allowing us to pinpoint the origin of the catalytic activity of e.g. a metal in terms of its electronic structure. However, the use of electronic structure theory as a tool for directly designing or searching for new materials is a rather expensive process [1] and has until now been extremely limited. The complexity arises to a smaller extent from the computationally expensive electronic structure calculations and to a larger extent from the enormous number of atomic configurations that might be considered when ordering even just a few atoms in a molecule or a few atoms in the unit cell of a crystalline system. In a few cases the underlying reactivity trends for a reaction have been understood well and were subsequently successfully used to computationally seek out new catalysts [2]. I here discuss the search for especially new hydrogenation catalysts [3,4]. The focus will be to show the generality of this trendand descriptor-based approach [5] by linking a few specific case stories to more fundamental underlying linear-energy relations for the adsorbate-surface bonds [6,7,8,9]. References: [1] G.H. Johannesson, T. Bligaard, A.V. Ruban, H.L. Skriver, K.W. Jacobsen, and J.K. Nrskov, Phys. Rev. Lett. 88, 255506 (2002) [2] J.K. Nrskov, T. Bligaard, J. Rossmeisl, C.H. Christensen, Nature Chemistry 1, 37 (2009) [3] M. P. Anderson, T. Bligaard, A. Kustov, K. E. Larsen, J. Greeley, T. Johannessen, C. H. Christensen, J. K. Nrskov, J. Catal. 239, 501 (2006) [4] F. Studt, F. Abild-Pedersen, T. Bligaard, R.Z. Srensen, C.H. Christensen, and J.K. Nrskov, Science 320, 1320 (2008) [5] J.K. Nrskov, T. Bligaard, and J. Kleis, Science 324, 1655 (2009) [6] J.K. Nrskov, T. Bligaard, A. Logadottir, S. Bahn, L.B. Hansen, M. Bollinger, H. Bengaard, B. Hammer, Z. Sljivancanin, M. Mavrikakis, Y. Xu, S. Dahl, and C.J.H. Jacobsen, J. Catal. 210, 275 (2002) [7] F. Abild-Pedersen, J. Greeley, F. Studt, J. Rossmeisl, T.R. Munter, P.G. Moses, E. Skulason, T. Bligaard, and J.K. Nrskov, Phys. Rev. Lett. 99, 016105 (2007) [8] E.M. Fernndez, P.G. Moses, A. Toftelund, H.A. Hansen, J.I. Martnez, F. Abild-Pedersen, J. Kleis, B. Hinnemann, J. Rossmeisl, T. Bligaard, and J.K. Nrskov, Angew. Chem. Int. Ed. 47, 4683 (2008) [9] T. Bligaard, Angew. Chem. Int. Ed. 48, 9782 (2009)

O1 Conversion of Sugars into Methyl Lactate using Lewis acidic Zeotype Catalysts
Martin Spangsberg Holm1,2, Shunmugavel Saravanamurugan1, Esben Taarning2 1 Center for Catalysis and Sustainable Chemistry, Technical University of Denmark 2 HaldorTopse A/S, 2800 Kgs. Lyngby Denmark E-mail: MSH@kemi.dtu.dk Abstract Significant attention has currently been devoted towards utilization of biomass derived substrates. We have investigated the isomerisation of C3-sugars in methanol into methyl lactate in an attempt to find a selective regenerable heterogeneous catalyst. Methyl lactate (lactic acid) has potential use as a platform chemical and may be upgraded to produce commodity chemicals. Recently, we reported the successful use of Lewis acidic zeolite/zeotype materials for this reaction with close to quantitative yields. Figure 1 presents catalytic data from batch experiments revealing a distinctively different reaction path when using purely Lewis acidic catalysts as compared to Brnsted acidic resins and conventional zeolites.

Figure 1. Yields of methyl lactate from various catalysts containing either a combination of or solely Brnsted or Lewis acidity. Reaction performed in methanol at 115 C for 24 h using 80 mg of catalyst and 1,25 mmol triose.

Additionally we discovered that at elevated temperatures the purely Lewis acidic zeotype catalyst, SnBeta, can give good yields (up to 68% for sucrose) of methyl lactate when converting either of the hexoses fructose, glucose or even sucrose. We propose a reaction path through a retroaldol condensation reaction of the hexoses forming two trioses which subsequently form methyl lactate. This reaction is similar to alkali degradation of hexoses with the advantage of being catalytic and could thus represent a new promising strategy. References [1] E. Taarning, S. Saravanamurugan, M.S. Holm, J. Xiong, R.M. West, C.H. Christensen, ChemSusChem, 2(7), 625-627, (2009). [2] R.M. West, M.S. Holm, S. Saravanamurugan, J. Xiong, Z. Beversdorf, E. Taarning, C.H. Christensen, J. Catal, 269(1), 122-130, (2010).

O2 Formic acid for vapour phase catalytic olefins hydrogenation

Dmitri A. Bulushev1, Sergei Beloshapkin2, Julian R. H. Ross1 1 CPI, CES, University of Limerick, Limerick, Ireland, 2 MSSI, University of Limerick, Limerick, Ireland E-mail: dmitri.bulushev@ul.ie Abstract Formic acid (FA) is a by-product of some second generation biorefineries, which transform non-food biomass to fuel additives [1]. Catalytic vapour phase transfer hydrogenation of olefins by FA (1) and hydrogen production from FA (2) have been studied: HCOOH + C2H4 CO2 + C2H6 HCOOH H2 + CO2 (1) (2)

A very small amount of a 10 wt.% Pd/C catalyst (6.8 mg) with the mean Pd particles size of 5.4 nm (HRTEM) catalyzed decomposition of FA and hydrogenation of ethylene by FA at temperatures as low as 358-433 K (Fig. 1). In hydrogenation, up to 95% of hydrogen from FA was consumed by ethylene for ethane formation. CO formation was negligible. The mechanism of hydrogenation by FA could involve the formation of adsorbed hydrogen from FA and its interaction with the olefin. The second step was fast. Effects of products on the FA conversion have been studied. As compared to the Pd catalyst, gold and copper supported catalysts were found to be less active in FA decomposition; neither hydrogenated the olefins. Hence, FA hydrogenated olefins over the Pd/C catalyst effectively, thus eliminating the need for a separate step of H2 production. This approach may have applications in deoxygenation reactions of some biomass derived chemicals necessary for the production of fuel additives.
1 0.8

a
C2H4 conversion HCOOH conversion

conversion

0.6 0.4 0.2 0 350

with C2H4 without C2H4

370

390

410

430

450

470

temperature, K

Figure 1. Conversions as a function of temperature for the decomposition of FA and hydrogenation of C2H4 by FA over the 10 wt.% Pd/C catalyst (6.8 mg). Total flow rate - 51 ml/min, 2.4 vol.% FA/He and 2.4 vol.% FA/1 vol.% C2H4/He, respectively

References [1] D.J. Hayes, S. Fitzpatrick, M.H.B. Hayes, J.R.H. Ross, in B. Kamm, P.R. Gruber and M. Kamm (Editors), Biorefineries-Industrial Processes and Products, Vol. 1, Wiley-VCH, Weinheim, 2006, p. 139.

O3 Process considerations for the catalytic dehydration of sugars to 5hydroxymethylfurfural

Jacob S. Jensen1, Wenjing Fu1, Troels B. Christensen2 and John M Woodley1,* 1 DTU Chemical and Biochemical Engineering, Technical University of Denmark, Lyngby 2 Novozymes A/S, Bagsvrd, Denmark *Email: jw@kt.dtu.dk Abstract Depletion of the fossil resources requires that new processes for the manufacture of the future chemicals from renewable resources are developed and implemented. On average, 75% of the mass of the organic components of biomass are carbohydrates, and thus transformation of carbohydrates into chemicals has a high potential for replacing fossil based chemicals [1]. Acid catalyzed dehydration of various sugars produces 5-hydroxymethylfurfural (HMF), a key intermediate for producing industrially relevant chemicals as illustrated in figure 1 [2]. Such carbohydrate-derived chemicals may cover a range of different applications, including building blocks for polymers, solvents, fuels and platform chemicals [3].
HO O OH OH OH OH dehydrate HO O ox. 2,5-furandicarboxylic acid O COOH levulinic acid O 2,5-dimehtyltetrahydrofuran HOOC O COOH

glucose HO O OH

CHO

rehydrate red.

5-hydroxymethylfurfural

OH OH OH fructose

Figure 1: Dehydration of sugars to 5-hydroxymethylfurfural, which can be converted to various products. The production of HMF from sugars has been investigated for a long time. Nevertheless only few attempts to implement the process on industrial scale are reported, which to some extent can be ascribed to challenges associated with the process [4]. In this work, various reaction and process options and challenges for the production of HMF from sugars are evaluated, with respect to both reaction performance, product recovery and reactor options. Important bottlenecks and strategies to overcome these are evaluated and used to identify the most promising process options and critical process parameters. References [1] [2] [3] [4] A. Corma, S. Iborra, A. Velty, Chem. Rev. 107, 2411 (2007). Y. Roman-Leshkov, J. N. Chedda, J. Dumesic, Science 312, 1933 (2006). A. Boisen et al., Chem. Eng. Res. Des. 87, 1318 (2009). B. F. M. Kuster, Starch 42, 314 (1990).

O4 Catalysts for sorbent enhanced reforming (SER) of methane in temperature swing reactors Kinetic
C. Sprung1, B. Arstad2, U. Olsbye1 1 University of Oslo, Dept. of Chemistry, P.O. 1033, 0315 Oslo, Norway 2 SINTEF Materials and Chemistry, Pb. 124, 0314 Oslo, Norway E-mail: christoph.sprung@smn.uio.no Abstract Hydrogen production by sorbent enhanced reforming (SER) of methane is an alternative reforming route with simultaneous CO2 capture inside the reactor [1]. Catalyst and sorbent (typically a metal oxide) are co-present inside a fluidized bed reactor system. In a first stage, the reformer (550 600 oC), CH4 and H2O are converted to H2 and carbon oxides. The latter ones are captured by the sorbent as CO2 (from water gas shift reaction) to form a solid carbonate. In a subsequent process step the sorbent is regenerated at about 900 oC. Thus, the products H2 and CO2 leave the process through separate streams. One of the challenges in SER is the catalyst development, it demands high activity towards steam methane reforming and withstand against the conditions present during sorbent regeneration. As a model system to study the kinetic behaviour during steam methane reforming, we chose a Ni/NiAl2O4 catalyst system. Kinetic studies are carried out by varying the space time in a fixed bed reactor under differential conditions between 550 and 600 oC (Fig. 1(A)). The determined reaction rates were compared to established micro kinetic models from the literature (Fig. 1(B)), derived from elementary reaction steps.

Figure 1: (A) CH4 & H2O conversion as a function of space time variation (0.01 gcat); (B) experimental reaction rate at 600 oC compared to established micro kinetic models [2-4] Out of the chosen micro kinetic models (Fig. 1(B)), Wei&Iglesia`s [3] follows the presented data best. However, modifications in the model are required to fit more precisely the present and also other experimental conditions. References [1] D. P. Harrison, Ind. Eng. Chem. Res., 47 (2008), 6486. [2] K. Hou, R. Hughes, Chem. Eng. J., 82 (2001), 311. [3] J. Wei, E. Iglesia, J. Catal., 224 (2004), 370. [4] J. Xu, G. F. Froment, AIChE, 35 (1989), 88.

O5 Kinetics of steam reforming over ruthenium based catalysts

Tommy L. Jrgensen1, Jon G. Jakobsen1, Ib Chorkendorff2, Stig Helveg1, Jens Sehested1 1 Haldor Topse A/S, Nymllevej 55, DK-2800 Lyngby 2 Center for Individual Nanoparticle Functionality (CINF), Department of Physics, Building 312, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark tolj@topsoe.dk Abstract Large scale production of liquid products like diesel and methanol in Gas-to-Liquid (GTL) plants has increased the interest for developing steam reforming catalysts that can operate at steam/carbon ratios where nickel catalysts form carbon whiskers [1]. Noble metals such as Ru, Rh, Ir, Pt and Pd do not form whisker carbon when applied at very low steam/carbon ratios. Ru is among the most active metals for catalyzing the methane steam reforming reaction [1,2]. Here, the steam and CO2 reforming activities of a Ru/ZrO2 catalyst were measured by varying the inlet partial pressures of CH4, H2, CO2 and H2O as well as the temperature. The reactivity was modeled by combining a reactor model and a kinetic model using methane dissociative adsorption as the rate limiting step. Furthermore, CO and H adsorbents were considered as being able to block the active surface. The kinetic expression for methane steam reforming over the Ru/ZrO2 catalyst is given by a Langmuir-Hinshelwood type expression [2]:
108 [ kJ mole ] mole 4.39 107 exp PCH 4 (1 SR ) RT g h bar 87 [ kJ mole ] 71[ kJ mole] 1 2 PCO + 7.31106 1 + 2.19 105 bar 1 exp bar 1 2 exp PH 2 RT RT
2

R=

The

Ru/ZrO2 catalyst was characterized using TEM and H2 chemisorption. ETEM had to be used for determining particle size distributions since ruthenium particles form a small amorphous ruthenium oxide surface layer of about 1 nm thickness when exposed to air at room temperature. The kinetic data are discussed in the context of the relative activities and kinetics of noble metals [1]. References [1] G. Jones, J.G. Jakobsen, S.S. Shim, J. Kleis, M.P. Andersson, J. Rossmeisl, F. Abild-Pedersen, T. Bligaard, S. Helveg, B. Hinnemann, J.R. Rostrup-Nielsen, I. Chorkendorff, J. Sehested, J.K. Nrskov, J. Catal. 259 (2008) 147-160. [2] J.G. Jakobsen, T.L. Jrgensen, I. Chorkendorff, J. Sehested, Appl. Catal. A 377 (2010) 158-166.

O6 Hydrogen generation from low-sulphur diesel over Rh-based metallic monolithic catalyst
Xanthias Karatzas1, Anglica Gonzlez 1, Jazaer Dawody 2, Lars J. Pettersson1 1 KTH Royal Institute of Technology, Department of Chemical Engineering and Technology, Teknikringen 42, SE-100 44 Stockholm, Sweden 2 PowerCell, Sven Hultins Gata 9D, SE-412 88 Gteborg, Sweden Abstract In this work we present results from hydrogen generation of low-sulfur diesel, via autothermal reforming (ATR), obtained with metallic monolithic catalysts consisting of 1 wt% Rh and 1:1 wt% Rh:Pt as active metals; La2O3, CeO2, ZrO2, Y2O3, Gd2O, MgO and MnO as promoters; -alumina and ceria-zirconia as supports; and FeCrAl alloy as carriers. The catalysts were prepared using the incipient wetness technique. The resulting powder samples were calcined at 800 C for 3 h and deposited on 400 cpsi FeCrAl alloy monoliths LS-type (d=18.0 mm, l=30.5 mm). The coating adherence strength of the catalysts was examined using thermal-shock and ultrasonic tests. Fresh powder samples of the catalysts were characterized by XRD, N2-BET, H2-chemisorption and H2-TPR analyses. The properties of the most promising catalysts are shown in Table 1. The activity results are also presented in the same table. A vertical steel tubular reactor, with diesel MK1 (S~6 ppm, C/H~6.43) as feedstock, was used for ATR. The operating parameters were T=650 C, H2O/C=2.5, O2/C=0.49, GHSV=17700 h-1 and P=1 atm.
Table 1. Catalyst properties and activity results. Catalyst Surface area (wt %) Rh1.0-Ce6.0Zr3.0Y1.0La10/-Al2O3 Rh1.0Pt1.0-Ce6.0Zr3.0Y1.0La10/-Al2O3 Rh1.0-Y5.0MgO4.0/CeO2-ZrO2 Rh1.0Pt1.0-Y5.0MgO4.0/CeO2-ZrO2 (m /g) 75 79 46 47
2

Pore volume (cm /g) 0.33 0.52 0.19 0.14

3

H/Rh (%) 27 n.a. 19 n.a.

Xdiesel (mol%) 95 96 94 94

H2 (vol%) 15 23 22 28

A seen in Table 1, the activity results show that 1:1 wt% Rh:Pt, in comparison to 1 wt% Rh, is more active towards hydrogen production. Furthermore, the effect of the support can also be observed. The results show that the CeO2-ZrO2 supported catalysts are more active in terms of hydrogen production. In general, ceria-zirconia, in particular ceria, as support material plays a major role in reforming as it can provide oxygen vacancies in the bulk that can remove carbon residues from the catalyst surface. In addition, it can also enhance the steam reforming activity during ATR which can result in higher hydrogen production, as seen in Table 1. Furthermore, the coating adherence strength tests also showed that the ceria-zirconia supports, in comparison to -alumina, was more strongly bonded with the FeCrAl alloy. The effects of the promoters in the CeO2-ZrO2 supported catalysts are currently being investigated. The aim of this study is to bridge the gap of knowledge concerning tailoring of diesel ATR catalyst formulations, in order to provide optimal performance during reforming and to reduce catalyst production cost e.g. lowering the noble metal loading in the washcoat. Our results indicate possibilities for the developed catalysts to be used in onboard vehicle fuel processing systems for energy efficient hydrogen production from diesel.

O7 Direct evidence of strong interaction between PtO nanoparticles and carbon nanofibers
Ingvar Kvande1,4, Stein Trygve Briskeby2, Nina Hammer1, Magnus Rnning1, John C.Walmsley3,4, Svein Sunde2, De Chen1* 1 Department of Chemical Engineering, 2Department of Materials Science and Engineering 3Department of Physics, Norwegian University of Science and Technology, N-7491 Trondheim, Norway 4 SINTEF Materials and Chemistry, N-7491 Trondheim, Norway * E-mail address: chen@chemeng.ntnu.no (De Chen) Abstract Metal-oxide particles supported on carbon nanofibers (CNFs) were studied by XANES and EXAFS. The samples were prepared by the metal-oxide colloid (MO) method [1-3]. The results indicated small Pt(O2) particles (< 1 nm) both before and after reduction. Identical PtO colloids were deposited onto fishbone (FB) and platelet (P) CNFs. Meanwhile, considerable differences were found in the Pt-Pt and Pt-C coordination for Pt supported on fishbone (MO/FB, 2,8 wt% Pt) compared to Pt supported on platelet CNFs (MO/P, 6,8 wt %). The results indicate that the deposition of smaller Pt particles, strongly coordinated and interacted with the CNF surface is realized on the FB support. In the case of MO/P, the Pt-Pt coordination from the first coordination shell after reduction is 6.1. A significantly lower Pt-Pt coordination of 2.7 was found for MO/FB. Moreover, the Pt-C coordination number for MO/P for the short interatomic distance was found to be 0.9, while it was 2.2 for MO/FB. Supporting data were found from cyclic voltammetry on similarly loaded catalysts (MO/P: 3,5 wt% Pt and MO/FB: 3,0 wt % Pt). The present results are ascribed to a difference in edge structure and nature of anchoring sites, the importance of which was indicated and discussed thoroughly for similar samples in a recent publication [3]. The results are considered to provide an explanation for the higher performance displayed by MO/P compared to MO/FB-catalysts in the H2-oxdation with and without the presence of CO [4]. The influence of the CNF structure on metal particle anchoring is thought to be a key issue in the understanding and future design of CNF supported catalysts. Table 1. Results from the EXAFS analysis.
Scatterer Pt-Pt Pt-Pt Pt-C Pt-C MO/FB Na R []b 2.7 2.71 0.6 3.87 2.2 2.18 3.8 2.64 22 [2]c 0.013 0.013 0.013 0.004 Scatterer Pt-Pt Pt-Pt Pt-C Pt-C Na 6.1 3.0 0.9 1.2 MO/P R []b 2.76 3.92 2.11 2.70 22 [2]c 0.012 0.018 0.007 0.010

N: 20%; R: 0.02 , a) Coordination number, b) Interatomic distance, c Debye-Waller type factor

References [1] M.T. Reetz, M. Lopez: U.S. Patent 7,244,688 (2003). [2] I. Kvande, S. Briskeby, M. Tsypkin, M. Rnning, S. Sunde, R. Tunold and D. Chen, Top. Catal., 45 81 (2007). [3] I. Kvande, J. Zhu, T.-J. Zhao, N. Hammer, M. Rnning, S. Raaen, J.C. Walmsley and D. Chen, J Phys. Chem. C, 114 1752 (2010). [4] I. Kvande, D. Chen, T.-J. Zhao, I. Skoe, J. Walmsley and M. Rnning, Top. Catal., 52 664 (2009)

O8 Microstructured reactors in compact conversion of natural gas and biomass to liquid fuels and hydrogen
Hilde Venvik1, Peter Pfeifer3, Rune Myrstad2, Ingrid Aartun1, Hamidreza Bakhtiary D.1, Fatemeh Hayer1, Xuyen Kim Phan1, Bjrn Christian Enger1, Rune Ldeng2, Oliver Grke3, Klaus Schubert3, Anders Holmen1. 1 Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway 2 SINTEF Materials and Chemistry, NO-7465 Trondheim, Norway 3 Karlsruhe Institute of Technology, D-76344 Eggenstein-Leopoldshafen, Germany E-mail: hilde.venvik@chemeng.ntnu.no Abstract Conversion of remote/stranded natural gas to distributable products may require technologies that meet different criteria than conventional steady-state industrial processes, particularly if to take place on platforms or ships. Such process equipment needs to be compact and lightweight, and stringent standards may exist with respect to safety and vibrations tolerance. Similar requirements exist in future biomass conversion into liquid fuels, where the transport of raw or pre-conditioned biomass to megascale plants over large distances may be unsustainable. Microstructured reactors, where reactions take place in parallelized channel or slit-like arrangements in the sub-millimetre range have been developed since the early 1990ies. They are prospected to increase efficiency relative to existing process technology because of their mass and heat transfer properties. In addition, they offer increased safety as well as options for developing completely new process windows. Forschungszentrum Karlsruhe, now part of the Karlsruhe Institute of Technology (KIT), has been a pioneering research environment with unique laboratories for microstructuring and assembly for development of microchannel process units (reactors, heat exchangers and mixers). The Norwegian University of Science and Technology (NTNU) and SINTEF Materials and Chemistry has since 2000 collaborated with KIT to explore the potential for microstructured reactors for hydrogen production and natural gas conversion. This contribution summarizes the results and recent progress of this research within partial oxidation and oxidative steam reforming of methane and propane to hydrogen/syngas, methanol synthesis and direct synthesis of dimethyl ether (DME). Typical reactor are shown in figure 1. It integrated micro packed bed reactor-heat exchanger is capable of operating up to 100 bar and practically isothermally in the strongly exothermic reactions.

Figure 1: A. Rh-impregnated microstructured monolith. B. Microreactor for methanol and DME. synthesis

O9 Application of microchannel reactors in the dehydrogenation of isobutane

Reetta Karinen, Sanna Airaksinen, Pivi Kiviranta, Outi Krause Aalto University School of Science and Technology, P. O. Box 16100, 00076 Aalto, Finland E-mail: Reetta.Karinen@tkk.fi Abstract Microchannel reactors have gained increasing interest recently. They provide e.g. efficient heat and mass transfer characteristics and high surface to volume ratio, which make them suitable for operating with fast, highly endothermic or exothermic reactions in submillimeter range. [1, 2] Sandwich-type structured microchannel reactors with chromia/alumina catalyst were investigated in the dehydrogenation of isobutane to isobutene. Reactor plate channels had been coated with -alumina and chromia was deposited on the alumina by the atomic layer deposition (ALD) method. Four microchannel reactors with different chromium loadings were tested, and their behavior was compared with ALD-prepared powder chromia/alumina catalysts. The morphology and the chemical composition of the catalyst phase were investigated by Scanning Electron Microscopy (SEM) coupled with Energy Dispersive X-ray analysis (EDX). The microchannel reactors were active in the dehydrogenation of isobutane at 570C under atmospheric pressure. In addition, the chromia phase in the microchannel reactor seems to have similar oxidation state distribution as the conventional powder catalyst. The conversion increased fairly linearly with the amount of chromium in the reactor which indicates that the chromium content increased as a function of ALD cycles and the deposited chromia was active and easily available for the dehydrogenation reaction. The selectivity to isobutene in microchannel reactor was over 90 mol-% which was clearly higher than in the experiments with chromia/alumina powder catalyst. When the selectivity is compared at a similar conversion level under the same operating conditions the selectivity in microchannel reactor was 25-40 percentage units higher compared to the powder catalyst. Compared to a similar study on Pt-Sn/Al2O3, we operated on lower conversion level but the difference in the selectivity between microreactor and powder catalyst was more distinct. [3] ALD is a promising method for adding active catalyst material in the microchannel reactor. Further, the high selectivity towards the desired reaction even at low conversion level makes the microchannel reactor attractive for measuring detailed kinetic data. References [1] [2] [3] G. Kolb, V. Hessel, Chem. Eng. J. 98, 1 (2004). L. Kiwi-Minsker, A. Renken, Catal. Today 110, 2 (2005). E. Novakova, N. Winterton, K. Jarosch, J. Brophy, Catal. Comm. 6, 586 (2005).

010 Photocatalytic measurements in -reactors

Peter C. K. Vesborg1*, Jakob L. Olsen1, Toke R. Henriksen2, Su-il In1, Ole Hansen2, and Ib Chorkendorff1
2

Department of Physics - CINF, Technical University of Denmark, Lyngby,Denmark Department of Micro and Nanotechnology, Technical University of Denmark, Lyngby,Denmark * E-mail: vesborgs@fysik.dtu.dk

Quantitative measurements of photocatalytic activity typically involve prolonged illumination of large amounts of catalyst coupled with (typically) gas-chromatographic product detection. As a complementary approach, we have developed a class of -reactors, fabricated in silicon using MEMS technology [1]. These -(flow)reactors are sealed by a transparent Pyrex lid and employ massspectrometric product detection making them ideal for photocatalytic measurements [2]. The combination of the tiny internal volume (~250 nl) of the -reactors and the detection speed of the mass spectrometer yields unprecedented time resolution (~1 s) with high sensitivity (~109 product molecules/s). We demonstrate how these reactors can be used to perform quantitative measurements of photocatalytic performance as a function of light intensity and as a function of wavelength. For anodically grown [3,4] TiO2 nanotubes and for P25 we find the CO-oxidation rate (in dry oxygen) to scale with illumination intensity to the power of 0.84 (Figure 1). Furthermore, we find that peak (internal) quantum efficiency for CO-oxidation over TiO2 nanotubes occurs between 330 nm and 355 nm for thin, back-illuminated films (Figure 2) [5].

Figure 2: Photocatalytic CO-oxidation as a function of illumination intensity (367 nm)

Figure 1: Photocatalytic Co-oxidation as a function of wavelength

References [1] Henriksen, T et al., Review of Scientific Instrument 80, 12 (2009) . [2] Vesborg, PCK et al, submitted, (2010) [3] In, Su-il et al., Accepted - Journal of the Electrochemical Society, 157, (2010) [4] Mor, GK et al., Solar Energy Materials and Solar Cells, 90, (2006) [5]Vesborg, PCK et al., submitted, (2010)

O11 Direct Decomposition of NO on C-type Cubic Rare Earth Oxides

Nobuhito Imanaka Department of Applied Chemistry, Faculty of Engineering, Osaka University 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan Email imanaka@chem.eng.osaka-u.ac.jp Abstract The emission of nitrogen oxides (NOx) has been, recently, strictly regulated, because they are not only harmful to human beings but also causing photochemical smog and acid rain. Among the NOx species in the exhaust gas emitted at elevated temperatures, the NO2 content is negligible and thermodynamically stable one is principally NO. Although various types of the NO reduction methods have been proposed, the direct decomposition of NO into N2 and O2 (2NO N2 + O2) is the ideal way for NO removal, because the process is simple and any reductants are not necessary. In the course of our research on the catalytic reduction of NO, we have found that C-type cubic rare earth oxides based on Gd2O3, (Gd1xyYxBay)2O3y (0 x 0.26, 0 y 0.08)[1], can exhibit higher activity for direct NO decomposition than those of the previously reported ones. In rare earth oxide series, there are three types of crystal structure, namely A- (hexagonal), B- (monoclinic) and C-type (cubic), according to the ionic radius of the individual rare earth element. The lattice volume of the rare earth oxides expands in the order of A-type < B-type < C-type with the corresponding element. As a result of it, the C-type structure holds the largest interstitial open space suitable for NO decomposition site among these three types. In particular, C-type (Y0.69Tb0.3Ba0.01)2O2.99+ realizes the 100 % NO conversion into N2 and O2 even at 1173 K as shown in Figure 1. In addition to this, the activity is still at high conversion ratio of 70.8 %, in the presence of 5 vol% oxygen, indicating that the present C-type cubic (Y0.69Tb0.3Ba0.01)2O2.99+ catalyst would be expected to be a novel candidate as a direct NO removal catalyst[2].

Figure 1: Temperature dependence of the NO conversion into N2 on (Y0.99xTbxBa0.01)2O2.99+ and on (Gd0.7Y0.26Ba0.04)2O2.96 catalysts (NO: 1 vol%; He balance; W/F = 3.0 g s cm-3) References [1] N. Imanaka, T. Masui, Chem. Rec. 9, 40 (2009). [2] S. Tsujimoto, K. Mima, T. Masui, and N. Imanaka, Chem.Lett. (2010) in press.

O12 H2 activation of aromatic hydrocarbons over Ag/Al2O3 diesel-SCR catalysts

H. Kannisto1, K. Arve2, H.H. Ingelsten1, K. Ernen2, M. Skoglundh1 and D.Yu. Murzin2 1 Competence Centre for Catalysis (KCK), Chalmers University of Technology, Sweden 2 Lab. Industrial Chemistry and Reaction Engineering, bo Akademi University, Finland E-mail: hannes.kannisto@chalmers.se Abstract In a prior study [1], silver alumina catalysts for HC-SCR were prepared by the freeze-dried sol-gel method [2]. The structure-activity relationship over the catalysts having varying Ag loading (2-14 wt.%) was studied using reducing agents of different structure and spatial geometry, e.g. octane, benzene, toluene and cumene. Characterization results from N2-adsorption, O2-chemisorption, SEM-EDXS, ICPSFMS and HRTEM were combined with flow reactor experiments. The results from the activity tests over Ag/Al2O3 catalysts with 2 (F2) or 6 (F6) wt.% silver are shown in Fig. 1 (open markers). The F2 catalyst showed higher maximum reduction activity than the F6 catalyst. However, when benzene, toluene or cumene was used as reductant, the F6 catalyst resulted in clearly higher NO to N2 conversion in the temperature range 400-450 C. From the results in this study [1], we concluded that the maximum NO to N2 reduction activity over Ag/Al2O3 catalysts depends on the silver loading and dispersion, but also on the nature and spatial geometry of the reductant. In the present study, we report the influence of the addition of 1000 ppm H2 to the feed. The results show a remarkable increase in NO to N2 conversion overall, especially for the F2 catalyst (Fig. 1, closed markers). The H2 addition removes the dependence on the silver particle size for the activity at low temperatures, most likely due to increased partial oxidation of the hydrocarbons [3]. The high silver loading of the F6 catalyst results in less reduction sites at low temperatures and increased combustion at higher temperatures, reducing the overall NO to N2 conversion, compared to the F2 catalyst.
100 90 80 NO to N2 conversion (%) 70 60 50 40 30 20 10 0 150 200 250 300 350 400 450 Temperature (C) 500 550 600

a)

NO to N2 conversion (%)

C8H18 + H2 C9H12 + H2 C 7H 8 + H 2 C 6H 6 + H 2

C8H18 C9H12 C7H8 C6H6

100 90 80 70 60 50 40 30 20 10 0 150

b)

C8H18 + H2 C9H12 + H2 C 7H 8 + H 2 C 6H 6 + H 2

C8H18 C9H12 C7H8 C6H6

200

250

300

350 400 450 Temperature (C)

500

550

600

Figure 1: NO to N2 reduction activity over a) F2 and b) F6 samples with (closed markers) or without (open markers) 1000 ppm H2 in the feed. Gas feed: 500 ppm NO, 375 ppm C8H18 or 333 ppm C9H12 or 430 ppm C7H8 or 500 ppm C6H6, 6 vol.% O2, 10 vol.% CO2, 350 ppm CO, 12 vol.% H2O and He as balance. GHSV=60 000 h-1. References [1]H. Kannisto, K. Arve, E. Olsson, H.H. Ingelsten, K. Ernen, M. Skoglundh and D.Yu. Murzin, In preparation. [2]H. Kannisto, H.H. Ingelsten and M. Skoglundh, J. Mol. Catal. A: Chem. 302, 86 (2009) [3]K. Shimizu, M. Tsuzuki, K. Kato, S. Yokota, K. Okumura and A. Satsuma, J. Phys. Chem. C. 111, 950 (2007)

O13 H2-promoted NOx adsorption/desorption over Ag/Al2O3: transient experiments and TPD study
N.A. Sadokhina1, D.E. Doronkin1, N.S. Telegina1, V.I. Bukhtiyarov2, A.Yu. Stakheev1 1 Zelinsky Institute of Organic Chemistry RAS, 119991, Leninsky Prosp. 47, Moscow, Russia 2 Boreskov Institute of Catalysis SB RAS, 630090, Prosp. Lavrentieva 5, Novosibirsk, Russia E-mail: st@ioc.ac.ru Abstract Ag/Al2O3 is one of the most promising catalysts for the selective catalytic reduction (SCR) of nitrogen oxides by hydrocarbons under lean-burn conditions. However, Ag/Al2O3 exhibits low SCR activity at T<300oC. It is known that addition of H2 is effective for enhancing SCR activity Ag/Al2O3 at 150-350oC. In view of an important role of NOx surface species in overall SCR process, in this study we investigated effect of H2 on the NOx adsorption/desorption at 120-400oC under conditions similar to those of SCR process (but in the absence of reductant). In addition to NOx adsorption/desorption experiments, temperature-programmed decomposition of model AgNO3/Al2O3 and Al(NO3)3/Al2O3 samples was studied for identification of surface nitrite-nitrate structures. It was found that introduction of H2 results in intensive NOx adsorption over Ag-species and alumina surface (see Figure). Dependence of the amount of adsorbed NOx on H2 partial pressure and adsorption temperature was studied in detail. Removal of H2 leads to decomposition of NOx species localized on Ag-sites (AgNO3-like structures). This decomposition is promoted by NO and results in intensive NO2 evolution. Removal of NOx species from alumina surface requires elevated temperature and occurs upon following temperature-programmed desorption. Upon continuous H2-supply, formation of AgNO3-like species followed by their decomposition by NO results in intensive NO2 formation. Evaluation of reaction kinetics suggests that the rate-limiting step of NO to NO2 oxidation over Ag/Al2O3 is the decomposition of AgNO3-like structures by NO. Hypothetical scheme of H2-promoted NOx adsorption/desorption over Ag/Al2O3 is presented in Figure.
Switch on H2 Concentration, ppm
NOx NO NO2

Switch off H2
NOx NO

400 300 200 100

NO2 0 0 60 120 180 240

Time, min Figure. Left: The effect of switching on and off hydrogen on the NOx concentration at 250oC. Catalyst loading: 2.124 g. Total gas flow: 500 cm3 min-1; 300 ppm NO, 7.5% O2, 10% CO2, (1000 ppm H2), balance N2. Right: Hypothetical scheme of H2-promoted NOx adsorption/desorption over Ag/Al2O3.

N. Sadokhina is grateful to Haldor Topse A/S for financial support in the framework of Ph.D. student support programme.

O14 Alkali resistant Fe-zeolite catalysts for SCR of NO with NH3

Siva Sankar Reddy Putluru1, Anker Degn Jensen1, Anders Riisager2, Rasmus Fehrmann*2. 1 Department of Chemical Engineering, Technical University of Denmark, Denmark 2 Department of Chemistry, Technical University of Denmark, Denmark E-mail address: rf@kemi.dtu.dk Abstract Fe-zeolite catalysts were prepared by ion-exchange method with HZSM5 (500 m2/g), HMOR (425 m2/g) and HBEA (680 m2/g) and iron nitrate solution. Catalysts prepared by this method were represented as Fe-ZSM5, Fe-MOR and Fe-BEA and tested for SCR of NO with NH3. Fe-zeolite catalysts showed high surface area and surface acidity which were essential for alkali resistivity in comparison with conventional metal oxide support like TiO2 and ZrO2 [1-2]. Fresh and potassium doped Fe-zeolite catalysts showed high activity during SCR of NO with NH3. Fe-zeolite catalysts were further compared with commercial vanadium catalyst (VWT) at various potassium concentrations to see the extent of deactivation. From Figure 1 it is observed that with increase of potassium concentration from 0-500 mol/g there is a gradual decrease in relative activity of Fe-zeolite catalysts, that of VWT catalyst is rapidly deactivated even at lower potassium concentration. The Fe-zeolite catalysts showed alkali resistance in the order of Fe-MOR>Fe-ZSM5>Fe-BEA. Fe-zeolite catalysts showed high surface acidity even at high potassium concentration (Table 1). This may indicate superior performance of Fe-zeolite catalysts for biomass fired SCR applications.

Figure 1: Relative activity of Fe-zeolite and VWT catalysts at different potassium concentrations. Table 1: Characterization results of Fe-zeolite catalysts.
Catalyst Fe-MOR Fe-ZSM5 Fe-BEA
1

Si/Al 10 15 25

Fe wt. % 3.0 3.2 5.6

K/Fe1

Fe/Al 0.38 0.58 1.60

0.93 0.87 0.49

Surface acidity (mol/g) Fresh potassium-doped1 1837 905 1286 660 1282 577

Potassium-doped catalysts are prepared with 500 mol/g of potassium References [1] Y. Zheng, A.D. Jensen and J.E. Johnsson, Appl.Catal.B 60, 253 (2005). [2] A. Kustov, M.Y. Kustova, R. Fehrmann and P. Simonsen, Appl.Catal.B 58, 97 (2005).

O15 Novel catalyst on a basis of immobilized horseradish peroxidase for biology active substances synthesis
1

V. Doluda, N. Lakina,V. Matveeva, M. Sulman Department of biotechnology and chemistry, Tver state technical university, 170026 Tver, Nab. A.Nikitina 22, Russia E-mail: doludav@yandex.ru

In recent years the use of the immobilized enzymes in industrial catalysis has considerably increased. There are the following major reasons for attaching enzymes to various supports: multiple or repetitive use of a single batch of enzymes; the ability to stop the reaction rapidly by removing the enzyme from the reaction solution; enzymes are usually stabilized by bounding, etc. While creating the reusable catalytic systems on the basis of enzymes one of the main problems is the choice of the firm carrier for immobilization of enzyme, which will provide its best stabilization [1, 2]. In this work various catalytic systems were investigated. Different type synthesized silica was used as the carrier and treated with chitosan, glutaric dialdehyde and carbodiimide. Two methods of chitosan and activating agent deposition on silica consecutive deposition and deposition of components mixture were studied. For the investigated catalysts optimal conditions for 2,3,6 trimethylphenol and methyl-naphthol (main intermediates in vitamin E and K synthesis) oxidation process with achievement of a high degree of conversion (more than 95 %) and high selectivity to target products (more then 98%) were found: temperature 37 , intensity of mixing 300 min-1, 6.5 - 7 for peroxidase, respectively. The optimal ratio of the components of catalytic systems was determined, and physicochemical investigations (FTIR spectroscopy, XPS, nitrogen physosorption) of optimal biocatalytic systems were carried out. Experiments shown, that consecutive deposition of chitosan on silica provides the strongest and stable bounding of enzyme with the carrier. During the experiments it was shown that glutaric aldehyde provides better stabilization of enzyme on the carrier in comparison to carbodiimide. Activity of synthesized catalyst was found to remains practically constant during repeated use. Kinetic and physicochemical investigations shown, that for the most active biocatalytic systems biopolymer (chitosan) is distributed on the surface of the carrier as separate molecules or bidimentional clasters. Such distribution promotes minimization of intradiffusive limitation during oxidation. The implementation of obtained results can present a new attractive possibility to change chemical stages of 2,3,6 trimethylphenol and methyl--naphthol oxidation in vitamin E and K synthesis for environmentally friendly enzymatic process. References [1] L.V.Bindhu, E.T.Abraham. Inc. J. Appl. Polym. Sci. 88 (2003) 1456-1464. [2] M.S. Ibrahim, H.I. Ali, K.E Taylor., N.Biswas, J.K.Bewtra. Water Environ. Res. 73 (2001) 165-172.

O16 High-Oleic Sunflower Oil as a One-Pot Reaction Feedstock for Dimethyl 1,19Nonadecanedioate Synthesis
Guido Walther1, Angela Kckritz1, Franz-Erich Baumann2, Frank-Martin Petrat2 and Andreas Martin1 1 Leibniz Institute for Catalysis, Albert-Einstein-Strae 29 A, D18055 Rostock, Germany 2 Evonik Degussa GmbH, Paul-Baumann-Strae 1, D45764 Marl, Germany E-mail: Angela.Koeckritz@catalysis.de Abstract For polymer synthesis, highly purified reactants such as ,modified hydrocarbon chains are required. With respect to sustainability and the environment, there is a keen interest to form such fine chemicals, i.e. dimethyl 1,19nonadecanedioate, from renewables and preferably in a one-pot reaction [1]. Inspired by the previous work of G.R. Eastham et al. on the methoxycarbonylation of lighter olefins [2], and that of D.J. Cole-Hamilton et al. on the methoxycarbonylation on unsaturated carboxylic acids and esters [3], we have focused on the direct synthesis of ,dimethyl nonadecanedioate from high-oleic sunflower oil. Our experiments show that this reaction proceeds highly selective to form dimethyl 1,19 nonadecanedioate, using Pd/bisdi(t-butylphosphinomethyl)-benzene, abbreviated Pd/DTMPMB, as catalyst. To our surprise, this one-pot reaction even bears a greater yield than one would expect applying the commercial two-step process of transesterification and a subsequent combined isomerisation/methoxy-carbonylation. We also show that this process is up scalable. The pattern of selectivity and activity, with respect to the catalyst structure, is often very complex. Certain ligands, however, have emerged as being particularly effective at certain reactions. The main reason for the unique properties that makes Pd/DTBPMB so active and selective for combined isomerisation/methoxycarbonylation reactions has not been elucidated yet. At first glance, it seems that Pd is the centre atom of a chelate complex [4], but there has also been suggested a doubly orthometallated structure [5], and that intermolecular attack of methanol may be important for such a process [4]. From a detailed ligand screening and a simple kinetic model of a potential reaction pathway of such a complex reaction, we may be support a mechanism for the synthesis of dimethyl 1,19 nonadecanedioate. References [1] [2] [3] [4] [5] M.A.R. Meier, J.O. Metzger and U.S. Schubert, Chem. Soc. Rev. 39, 1788 (2007). G.R. Eastham, C. Jimnez-Rodrigues and D.J. Cole-Hamilton, WO 2004014834-A1 (2004). C. Jimnez-Rodrigues, G.R. Eastham and D.J. Cole-Hamilton, Inorg. Chem. Commun. 8, 878 (2005). S.M.A. Donald, S.A. Macgregor, V. Settels, D.J. Cole-Hamilton and G.R. Eastham, Chem. Commun. 562 (2007). W. Clegg, G.R. Eastham, M.R.J. Elsegood, R.P. Toose, X.L. Wang and K. Whiston, Chem. Commun. 1877 (1999).

O17 Effect of biomass derived synthesis gas impurities on TOF and hydrocarbon selectivity in cobalt Fischer-Tropsch synthesis
yvind Borg, Nina Hammer*, Bjrn Christian Enger*, Sigrid Eri, Torild Hulsund Skagseth, Erling Rytter Statoil Research Center Trondheim, NO-7005 Trondheim, Norway * Present address: Department of Chemical Engineering, Norwegian University of Science and Technology (NTNU), NO-7491, Trondheim, Norway. E-mail: err@statoil.com (Erling Rytter) Abstract The effect of typical biomass derived synthesis gas impurity elements (Na, K, Ca, Mg, Cl, Mn, Fe, P, S) on cobalt Fischer-Tropsch catalyst performance was investigated in fixed-bed reactors at 210C, 20 bar, and H2/CO = 2.1. All 22 catalysts were prepared by incipient wetness impregnation of different supports (-Al2O3, modified alumina, SiO2, TiO2) with aqueous solutions of cobalt nitrate hexahydrate and perrhenic acid. Small amounts (0-1000 ppm) of impurity precursors were added ex situ either in the same impregnation step (co impregnation) or in a later step (post impregnation). The effect of sulphur was studied in situ by introducing a H2S containing synthesis gas. Before use, the catalysts were characterised by N2 sorption, TEM, H2 chemisorption, propene chemisorption, and TPR. The presence of alkali (Na, K) and earth alkaline elements (Ca, Mg) decreased the activity dramatically. The effect was observed at ppm levels and was independent of support or impregnation order. H2 and propene chemisorption, however, showed that the number of active sites after reduction was unaffected. Thus, the TOF was lower for these catalysts (Figure 1a). The results point to electronic effects rather than blocking of active sites. Alkali and alkaline earth metals increased and decreased the C5+ selectivity, respectively. Small amounts (400 or 800 ppm) of Mn, Fe, and P had only minor effects on the catalyst performance. Presence of Cl (400 ppm) decreased the Co surface area, but gave the same activity as the unmodified catalyst. Thus, the TOF was higher for this catalyst. Addition of S affected the activity negatively at all studied concentration ranges (2.5, 5, and 10 ppm S in the synthesis gas). When taking the lowered CO conversion levels into consideration, S did not significantly impact the C5+ selectivity (Figure 1b). Thus, S seems to merely block active sites and leave the remaining sites unchanged.
H2 chem. C3H6 chem.
134 131 100 100 77 54 55 79 60 64 103 101 107 99

0 ppm S

2.5 ppm S

5 ppm S

10 ppm S

140

85

Normalised turnover frequency

120 100 80 60 40 20 0

94 93

101 101

C 5+ selectivity (%)

84 83 82 81 80 79 78 77 76 75 0 5 10 15 20 25 30 35 40 45 50

None

Na

Mg

Ca

Mn

Fe

Cl

Element

CO conversion (%)

(a)

(b)

Figure 1: Normalised TOFs of unmodified ( 1) and modified catalysts (400 ppm Na, K, Mg, Ca, Mn, P, Cl, 800 ppm Fe). The grey and white columns are based on hydrogen chemisorption numbers and propene chemisorption numbers, respectively (a). C5+ selectivity vs. CO conversion during the H2S addition experiment (b).

O18 On the selectivity of cobalt-based Fischer-Tropsch catalysts

Sara Lgdberg1, Matteo Lualdi1, Gabriella Di Carlo2, Sven Jrs1, Magali Boutonnet1, John C. Walmsley3, Edd A. Blekkan4, Erling Rytter4,5, Anders Holmen4 Royal Institute of Technology (KTH), Chemical Technology, Teknikringen 42, 100 44 Stockholm Sweden 2 ISMN-CNR-Monterotondo Stazione, Rome, Italy 3 SINTEF Materials and Chemistry, NO-7469 Trondheim, Norway 4 NTNU, Department of Chemical Engineering, Trondheim, Norway 5 StatoilHydro Technology Centre Trondheim, Trondheim, Norway E-mail: lualdi@kth.se Abstract 37 cobalt-based supported catalysts, differing in support material (-Al2O3, -Al2O3, TiO2, SBA-15), Co loading (4 - 30 wt%), promoters (none, Re or B), Cl content, Co particle size (larger than ~6 nm), morphology and degree of reduction, were investigated in the Fischer-Tropsch reaction. Three different preparation techniques were used; incipient wetness impregnation (IW), wetness impregnation (WI) and microemulsion (ME). Furthermore, three catalysts were exposed to hydrothermal treatment after being prepared by the IW or ME techniques. The catalytic tests were performed in a fixed-bed reactor at the following reference case process conditions: 483 K, 20 bar, molar H2/CO ratio = 2.1, pellet size: 53-90 m. The effect of adding water vapour to the feed was investigated for 20 of the catalysts, and a lower H2/CO ratio (1.0) was tested for some catalysts. Chain-growth probabilities for Cn* surface intermediates, Cn values, were calculated for n = 1 - 4. Figure 1 shows that the C-atom selectivities and Cn values for the non-ASF distributed products (i.e. ~ C1 - C4) fit to linear correlations irrespective of the properties of the catalysts, and furthermore indicates that C1 is more or less invariant with SC5+ at reference case process conditions. These observations will be discussed in terms of possible mechanisms and selectivity-governing parameters.
20 18 16
SC1, B
R2 = 0.9562

1.0

SC2, B SC3, B SC4, B

0.9

C2

R2 = 0.5674

SC1 - SC4 (CO2-free) [%]

14 12 10 8 6 4 2 0 55 60 65 70 75 80 85
R = 0.8223
2

R2 = 0.9793

0.8

R = 0.9776

C1 - C4

C3
0.7

R2 = 0.9658

C4
0.6

R2 = 0.9829

0.5

C1

R2 = 0.1485

90

0.4 50 55 60 65 70 75 80 85 90

SC5+ (CO2-free) [%]

SC5+ (CO2-free) [%]

Figure 1: SC1 - SC4 and Cn values (n = 1 - 4) vs SC5+ for all catalysts in period A (gray symbols) and B (white/colored symbols) at reference case process conditions. CO conversions in period A vary between 3.5% and 30%. CO conversion in period B is 40%. Regression lines are based on data points obtained in period B.

O19 In-situ & Operando spectroscopic methods for studying industrial applications and deactivation phenomena of modified vanadium oxide catalysts for the NH3-SCR reaction
Sren Birk Rasmussen1, Johannes Due-Hansen2, Ewelina Mikolajska1, Miguel Angel Baares1, Pedro vila1, Rasmus Fehrmann2 1 Instituto de Catlisis y Petroleoqumica, C.S.I.C. 28049-Madrid, Spain 2 Centre for Catalysis and Sustainable Chemistry, DTU Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark Abstract Interaction between industrially relevant gas mixtures and VOX catalysts on TiO2 and ZrO2-SO42supports has been studied by means of Operando Raman- and in-situ EPR spectroscopy. In this work we use of in-situ techniques for obtaining information on the catalytic chemistry of oxo vanadium species during perturbations invoked by exposure to gas compositions relevant for industrial installations of SCR units. The Vv=O stretching mode and the bridging oxygen in the VOV bond is monitored by Operando Raman and/or UV-vis spectroscopy, while VO2+ surface species are evaluated in-situ by high temperature EPR spectroscopy. The combination of multiple techniques applied at relevant temperatures and gas conditions allows for a detailed analysis of the influence of changes in the gas phases in the industrial boilers. Examples of industrial relevance are potassium containing fly ash present in the offgas from biomass fired power plants [1], and hydrogen/oxygen mixtures exposed to the SCR units in the tail pipe of waste boilers [2]. In the figure below, a series of Raman spectra shows that at 250C, no change in redox properties of vanadium is achieved by switching between a 3.5% O2 and a 2%H2/8%O2 gas mixture. The in-situ EPR spectra to the right reveal that the SCR gas (3.5% O2, 2.7% H2O, 1000 ppm NO & NH3) indeed reduces V(V) to VO2+ - and that subsequent exposure to 2%H2/8%O2 almost eliminates these VO2+ bands. The SCR equilibrium is again restored upon switching back to the SCR gas mixture.

Figure 1: In-situ Raman spectra (left) and EPR(right) of a VOX-WO3/TiO2 catalyst at 250C, exposed to different gas phases. References [1] Y. Zheng, A.D. Jensen, J.E. Johnsson, J.R. Thgersen, Appl. Catal. B: Environmental, 83, 186 (2008). [2] S.B. Rasmussen, A. Kustov, J. Due-Hansen, B. Siret, F. Tabaries, R. Fehrmann, Appl. Catal. B: Environmental, 69, 10, (2006).

O20 Catalytic conversion of syngas into mixed long-chain alcohols over cobaltmolybdenum sulfide
Jakob Munkholt Christensen1, Peter Arendt Jensen1, Anker Degn Jensen1 1 Department of Chemical and Biochemical Engineering, Technical University of Denmark E-mail: aj@kt.dtu.dk Abstract This work is an investigation of how the process conditions influence the catalytic conversion of syngas into mixed alcohols over potassium promoted cobalt-molybdenum sulfide. Because of their high octane numbers alcohols are interesting as additives to or substitutes for oil-derived gasoline. By virtue of a superior miscibility with gasoline a mixture of methanol and/or ethanol with higher alcohols may however be more easily integrated into the existing infrastructure than pure methanol or ethanol [1]. Such a mixture of alcohols can be formed directly from syngas over various catalysts. A potential catalyst for the alcohol synthesis is alkali promoted MoS2 preferably additionally promoted with Co or Ni [2]. Presently it is investigated how the composition of the syngas feed influences the behaviour and the structure of the sulfide catalyst. It is also investigated how the addition of ethanol to the feed affects the catalytic properties. As shown in figure 1 the production of 1-butanol benefits the most from addition of ethanol to the syngas. This could indicate that one route to chain growth for this catalyst is the coupling of alcohols here exemplified by the coupling of ethanol or ethanol-derived species into 1butanol. Such coupling reactions have not previously been reported for this type of catalyst.
0.14 0.12 0.1 0.08 0.06 0.04 0.02 0 0 1 2 3 4 Ethanol fraction in feed [mol%] 5 6 iso-Butanol 1-Propanol Methanol

Alcohol productivity [g (g cat.) h ].

-1

1-Butanol

Figure 1: Production rates for different alcohols as functions of the ethanol concentration in the syngas feed [3]. The experimental conditions are: T = 325.3 C, P = 100 bar, GHSV = 5500 h-1. Feed before ethanol addition: 49.1 vol % H2, 50.9 vol% CO. Time on stream is +30 h. References [1] J. L. Keller, Hydrocarbon Process. 58, 127 (1979). [2] C. B. Murchison, M. M. Conway, R. R. Stevens and G. J. Quarderer in Proceedings of the 9th International Congress of Catalysis (Eds.: M. J Phillips and M. Ternan) Vol. 2 p. 626. Chemical Institute of Canada, Canada, 1988. [3] J. M. Christensen, P. A. Jensen, N. C. Schidt and A. D. Jensen, ChemCatChem, In press.

-1

O21 Lean NOx reduction with various bio-diesels as reducing agents

Sara Erkfeldt1,2, Anders Palmqvist2 1 Volvo Technology Corporation, Chalmers Science Park, SE-412 88 Gteborg, Sweden 2 Competence Centre for Catalysis, Chalmers Univ. of Tech., SE-412 96 Gteborg, Sweden E-mail: sara.erkfeldt@volvo.com Abstract The demand for renewable fuels is expected to increase in the future. This in part driven by the increased price and limited resources of crude oil, but the main driver is the concern about climate change and the need to reduce the carbon dioxide emissions. In diesel vehicles, bio-diesels can be used alone as a replacement for fossil based diesel fuel (B100) or in various blends with fossil diesel (e.g. B15 with 15% bio-diesel). Although the emissions of particula-tes, carbon monoxide and hydrocarbons are lower, the NOx emissions are increased with bio-diesels compared to conventional diesel [1]. Therefore, aftertreatment technologies for NOx reduction under lean conditions are needed. One promising method for lean NOx reduction is selective catalytic reduction by hydrocarbons in the fuel (HC-SCR). The type of hydrocarbon used as reducing agent is very critical to the activity of the catalyst. For an engine running on an alternative fuel it is essential to investigate the effect on the catalyst performance with this fuel compared to conventional diesel. However, only a limited amount of research has been published on HC-SCR when used with bio-diesel and synthetic diesel fuels [2-6]. In this work experiments were performed in a synthetic exhaust gas bench to investigate the influence of bio-diesels and synthetic diesel on the performance of two commonly used lean NOx catalysts. The catalysts were based on Ag/Al2O3 and Cu-ZSM-5, respectively. Seven different fuels were used as reducing agents; RME, B30, B15, GTL, NExBTL, Agrodiesel 15, and MK1 (Swedish Environmental Class 1), where the last one was used as reference fuel. Tests were also made with n-octane, used as a model reducing agent. The NO reduction activity at steady-state was evaluated at temperatures between 500-250C and at HC1/NOx-molar ratios between 2 and 8. The experiments showed that the NOx reduction activity variations, with the various alternative fuels tested, were moderate. The temperature dependence was quite similar, especially over Cu-ZSM-5. Somewhat larger variations between the fuels were observed with the Ag/Al2O3 catalyst. It was also concluded that the Cu-zeolite catalyst showed a higher activity at lower temperature than the Ag/Al2O3 catalyst for all alternative fuels tested. Thus, the active temperature window of the Cu-zeolite catalyst corresponds better to the temperatures of diesel engine exhaust. References [1] G. Knothe, C.A. Sharp, and T.W. Ryan Iii, Energy and Fuels 20 (2006) 403. [2] K. Arve, K. Eranen, M. Snare, F. Klingstedt, and D.Y. Murzin, Top. Catal. 42-43 (2007) 399. [3] V. Houel, P. Millington, R. Rajaram, and A. Tsolakis, Appl. Catal., B 73 (2007) 203. [4] X.Y. Shi, Y.B. Yu, H. He, S.J. Shuai, H.Y. Dong, and R.L. Li, J. Environ. Sci. 20 (2008) 177. [5] K. Suzuki, M. Haneda, and H. Hamada, J. Jpn. Pet. Inst. 52 (2009) 60. [6] J. Rodrguez-Fernndez, A. Tsolakis, R.F. Cracknell, and R.H. Clark, Int. J. Hydrogen Energy 34 (2009) 2789.

O22 Special characteristics of dimethyl ether as reducing agent in continuous lean NOx catalysis
Stefanie Tamm1,2, Hanna Hrelind Ingelsten1,2, Anders E. C. Palmqvist1,2 1 Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Gteborg 2 Applied Surface Chemistry, Chalmers University of Technology, SE-412 96 Gteborg E-mail: stamm@chalmers.se Abstract The interest in research and investments in alternative fuels has increased over the last years due to the concern for global climate change caused by increasing atmospheric CO2 concentrations and the limited fossil fuel resources available to support the growing energy demand. Dimethyl ether (DME) is one of the most energy effective alternative and low CO2 emitting fuels when produced from biomass gasification [1, 2]. Similar to other vehicles with combustion engines, vehicles running on DME will most likely need after-treatment technologies for a further reduction of NOx emissions to meet the most stringent upcoming legislations. One attractive technique would be selective catalytic reduction with DME (DME-SCR) as reducing agent. Here we show that, dimethyl ether is a special reducing agent since it induces radical reactions in the gas phase before the catalyst in the presence of O2 and NO above 300 C. Dimethyl ether dissociates into two radicals that start a chain of reactions in the presence of O2 and NO, resulting in NO2, CO, formaldehyde and formic acid as the main products. However, no clear reduction of NOx to N2 was observed. The occurrence of gas phase reactions put thus extra design criteria on an efficient DME-SCR catalyst. Despite these special conditions, good activity was achieved for NOx reduction with DME over a Al2O3 catalyst. Over this catalyst, NOx reduction starts at the same temperature as the gas phase reactions. This indicates an impact of the gas phase reactions on the NOx reduction over -Al2O3 that will be discussed. The formation of NO2 in the gas phase reactions can be expected to boost the activity for NOx reduction, since NOx conversion has been shown to be higher with NO2 than with NO in the gas mixture over -Al2O3 catalysts. On the other hand, the effect of the gas phase reactions can be simplified as partial oxidation of DME with parallel formation of CO. From this viewpoint, the gas phase reactions are expected to have a negative impact on the overall NOx reduction. References [1] [2] P. Ahlvik, . Brandberg, (2001) Well-to-wheel efficiency for alternative fuels from natural gas and biomass, 1 edn. Swedish National Road Administration, Borlnge, pp 1121. http://www.vv.se/filer/publikationer/2001-85.pdf. Accessed 10 Nov 2007. R. Edwards, J.-F. Lariv, V. Mahieu, R. Rouveirolles, Well-to-wheels analysis of future automotive fuels and powertrains in the European context, http://ies.jrc.cec.eu.int/wtw.html. Accessed 9 July 2007.

O23 Epoxidation of Olefins Catalyzed by the Cobalt based Metal-Organic Framework STA-12(Co)
Matthias J. Beier1,2, Wolfgang Kleist2, Michael T. Wharmby3, Paul A. Wright3, Reinhard Kissner2, Jan-Dierk Grunwaldt1,4, Alfons Baiker2 1 Technical University of Denmark, Lyngby, Denmark 2 ETH Zurich, Switzerland 3 University of St. Andrews, UK 4 Karlsruhe Institute of Technology (KIT), Campus North, Germany E-mail: mjb@kt.dtu.dk Abstract Unlike many oxidation reactions the catalytic olefin epoxidation using oxygen as the oxidant still requires sacrificial reductants such as aldehydes or the substrate itself. Alternatively, the epoxidation can be performed in DMF or similar solvents where no sacrificial additives are required [1]. Previous studies suggest Co-substituted zeolites to be suitable catalysts if Co is mainly present within isolated sites [1-3]. However, the low Co loading in zeolites requires high catalyst amounts. Metal-organic frameworks (MOFs) also possess the feature of isolated sites but at the same time have a far higher metal loading. With stilbene and styrene as model substrates (Scheme 1), we investigated the catalytic potential of a Co-based MOF, STA-12(Co). STA-12(Co) turned out to be considerably more active than Co3O4 and performed similar to Co-substituted zeolites reported in the literature at an absolute catalyst amount 100 times lower. According to a widely accepted mechanism, the aerobic liquid phase epoxidation in the presence of a sacrificial additive proceeds via a peroxo radical species while little is known about the reaction in DMF. Numerous tests with radical scavengers suggest that the reaction also depends on radical species but especially the role of the catalytically active Co is still under debate. We therefore performed in situ studies with X-ray absorption spectroscopy and electron paramagnetic resonance in order to get a more fundamental understanding of the underlying mechanism.

Scheme1: Epoxidation of styrene and (E)-stilbene using STA-12(Co) as a catalyst in comparison to Co3O4. References [1] Q. Tang, Y. Wang, J. Liang, P. Wang, Q. Zhang, H. Wan, Chem. Commun. 440 (2004). [2] Q. Tang, Q. Zhang, H. Wu, Y. Wang, J. Catal. 230, 384 (2005). [3] X. Y. Quek, Q. Tang, S. Hu, Y. Yang, Appl. Catal. A 361, 130 (2009).

O24 Cobalt complexes with tripodal ligands in oxidation catalysis

Susanne Mossin Department of Chemistry, CSC, Building 207, DTU, 2800 Lyngby, Denmark E-mail: slmo@kemi.dtu.dk Abstract Dioxygen is highly attractive as a renewable oxidant in oxidation catalysis. Molecular oxygen exists in the unreactive triplet spin state. In order for dioxygen to participate in oxidation reactions a suitable catalyst must be present. In biology transition metal ions provides the solution through the accessible redox potentials and electronic properties. Especially iron, manganese and copper is present in biologically important enzymes but although not extensively used in biology cobalt has unique properties that can be utilised industrially. Molecular cobalt complexes as the well-known cobalt salen complexes are known to coordinate molecular dioxygen in an end-on or bridging fashion and thus to activate the dioxygen molecule towards substrate oxidation. A series of tetradentate tripodal ligands featuring the same functional groups as salen have been synthesized and a number of complexes with cobalt, iron and manganese isolated. Due to steric control of the coordination environment the cobalt(III) centre is kept in the much more labile paramagnetic triplet state compared to the usual kinetic inert diamagnetic ground state of cobalt(III). These complexes as well as the analogous complexes of iron and manganese have been tested in a range of oxidation reactions relevant for sustainable production of chemicals. Examples include the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) being highly relevant for the replacement of petroleum-based building blocks in the plastic industry.

O25 Oxidation of DCM and PCE laboratory vs. industrial scale study
Satu Pitkaho, Satu Ojala and Riitta L. Keiski Department of Process and Environmental Engineering, University of Oulu, Finland E-mail: satu.pitkaaho@oulu.fi Abstract Chlorinated volatile organic compounds, CVOCs are widely used in industry and due to their harmful properties the release of CVOC is controlled by increasingly stringent regulations [1,2]. Catalytic oxidation is a promising CVOC abatement technology to meet the environmental and economic requirements [3]. The aim of this research was to find out a reliable laboratory scale research method for further catalyst development and reactor design purposes. The studied industrial scale incinerator is operating in the abatement of emission mixtures containing e.g. dichloromethane (DCM), perchloroethylene (PCE), dimethylformamide (DMF), toluene and ethanol. The incinerators normal operation temperature is 400-500C and the temperature is increased to 500600C when the emission contains PCE. The actual surface temperature of the catalyst is higher and changing periodically due to the flow reversal. The gas hourly space velocity (GHSV) of the incinerator is max. 16 000 h-1. The screening of the catalyst at laboratory scale was studied with the aid of 1) light-off tests and 2) constant temperature tests. The model compound used was DCM or PCE with the concentration of 500 ppm and 100 ppm, respectively. The GHSV used was 16 000 h-1, and the tests were carried out in moist (1.5 vol-% water) conditions. With DCM the transient light-off tests gave slightly more comparable results than constant temperature experiments compared to industrial measurements (Figure A). The overall conversions of PCE measured in industry were higher than in the laboratory scale and the constant temperature experiments followed industrial measurements better than light-off tests (Figure B). The comparison of industrial and laboratory scale experiments is not straightforward. For example the fact, that industrial emissions are often mixtures affects the oxidation results of single compounds and that complicates the real catalyst development. B A

Figure A) DCM and B) PCE conversions measured in industry with different VOCs in air (GHSV 16 000 h-1) and at laboratory scale; ligh-off and constant temperature (DCM 500 ppm and PCE 100 ppm in air, GHSV 16 000 h-1, water 1.5 vol-%). References Koyer-Golkowska et al. Catal Today 90, 133-138 (2004). [1] [2] Directive 99/13/EC. Official Journal of the European Communities, 29.3.1999. [3] Everaert & Baeyens, J Hazard Mater B109, 113-139 (2004).

O26 Kinetics of selective oxidation of sugars over gold catalysts

Bright Kusema1, Olga Simakova1, Pivi Mki-Arvela1, Tapio Salmi1, Dmitry Murzin1 1 Process Chemistry Center, bo Akademi University, FI-20500 bo/Turku, Finland E-mail address: bright.kusema@abo.fi Abstract Chemicals derived from various renewable sources have drawn great interest due to their features such as ability to produce biodegradable and biocompatible new products as well as value-added chemicals. Arabinogalactans (AG) are hemicelluloses found in large quantities in larch species and they account for 15-25 weight % of dry wood material. The average ratio of galactose, arabinose and glucuronic acid in AG is about 5:1:0.08. AG can be converted into valuable products by a two step approach, which includes hydrolysis of AG to monomers and catalytic transformation of the sugars into bio-based valuable products having many applications in the food, detergent, pharmaceutical and cosmetic industries [1, 2]. The focus of this research was on kinetics of selective oxidation of arabinose and galactose to arabinonic and galacturonic acid respectively over supported gold nanoparticles. Au catalysts were prepared by direct ion exchange, deposition with urea and impregnation. The catalysts were characterized by ICP, TEM and XPS. The influence of reaction parameters such as oxygen flow rate (2.55.0 ml/min), pH (6 10) and temperature (6090C) were investigated. The activities and initial rates of the catalysts studied showed a strong dependence on the pH of the reaction medium with slightly alkaline conditions and moderate temperatures exhibiting high conversion and selectivity. Figure 1 shows the kinetic curves of arabinose oxidation by 2% Au/Al2O3 at pH 8 and 60C. The effect of Au particle size on the activities and initial rates was also elucidated.
0,12

0,10

Arabinose Arabinolactone Arabinonic acid

0,08

C, mol/l

0,06

0,04

0,02

0,00 0 50 100 150 200

Time, min

Figure 1: Kinetics of selective oxidation of arabinose over 2% Au/Al2O3. References [1] B. T. Kusema, C. Xu, P. Mki-Arvela, S. Willfr, B. Holmbom, T. Salmi, D. Y. Murzin, I. J. Chem. Reactor Eng.. 8, A44 (2010). C. Baatz, U. Pre, Catal. Today. 122, 325-329 (2007). [2]

027 Selective gold-catalysed aerobic oxidations under ambient conditions

Sren Kegns1, Uffe V. Mentzel1, Jerrik Mielby1, Esben Taarning2, Kresten Egeblad2, Claus H. Christensen2, Anders Riisager1 1 Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby, Denmark 2 Haldor Topse A/S, Nymllevej 55, 2800 Kgs. Lyngby, Denmark E-mail: skk@kemi.dtu.dk Abstract In organic chemistry oxidation is a key reaction for conversion of functional groups. However, many of these oxidations are usually carried out using stoichiometric amounts of high-valent metal oxides, e.g. manganese or chromium oxides, which produce a huge amount of waste. To provide a practical and environmentally friendly alternative to these classical oxidations we have invested considerable effort in the development of catalytically aerobic oxidations. Here we present our results on the aerobic oxidation of alcohols, aldehydes and amines using gold nanoparticles supported on different composite materials (Figure 1). By applying different reaction conditions and substrates we were able to selectively (>90%) form carboxylic acids [1], esters [2], amides [3] and imines [4], respectively. The reactions were optimized to be as close to ambient conditions as possible.

Figure 1: Reaction schemes for the aerobic oxidation of alcohols and aldehydes References [1] C. H. Christensen, B. Jrgensen, J. Rass-Hansen, K. Egeblad, R. Madsen, S. K. Klitgaard, S. M. Hansen, M. R. Hansen, H. C. Andersen, A. Riisager, Angew. Chem. Int. Ed., 45, 4648 (2006). [2] C. Marsden, E. Taarning, D. Hansen, L. Johansen, S. K. Klitgaard, K. Egeblad C. H. Christensen, Green Chem., 10, 168 (2008). [3] S. K. Klitgaard, K. Egeblad, U. V. Mentzel, A. G. Popov, T. Jensen, E. Taarning, I. S. Nielsen, C. H. Christensen, Green Chem., 10, 419 (2008) [4] S. Kegns, J. Mielby, U. V. Mentzel, C. H. Christensen, A. Riisager, submitted.

O28 Using TPD data in determination of ammonia sorption kinetics on HZSM-5

Kouva, S. K.1, Kanervo, J. M.1, Krause, A. O. I.1, Schler, F.2, Olindo, R.2, Lercher, J. A.2 1 Aalto University School of Science and Technology, P.O. Box 16100, 00076 Aalto, Finland 2 TU Mnchen, Catalysis Research Center, Lichtenbergstrae 4, 85747 Garching, Germany E-mail: sonja.kouva@tkk.fi Abstract MFI zeolites are widely used especially in petrochemical and refinery processes. Their ability to catalyze hydrocarbon transformations is associated to their acidity, which can be modified by tuning the Si/Al ratio of the zeolite. Temperature-programmed desorption (TPD) is one technique often implemented for the characterization of acid/base properties. In the present work, ammonia sorption on a HZSM-5 sample with Si/Al=45 was studied using a vacuum-TPD setup. First, the zeolite sample (50 mg, particle diameters 0.28-0.50 mm and 0.71-1.0 mm) was pretreated in vacuum at 450 C for 1 h. Ammonia was adsorbed at 100 C or 200 C and excess ammonia was evacuated for 2 h. TPD was carried out by heating the reactor in vacuum from adsorption temperature up to 770 C at a rate of 7, 12, or 17 C/min. Desorbed ammonia was detected using MS (m/z+=16) and calibrated with microgravimetry. Microgravimetric measurements show the amount of desorbed ammonia (Tads = 100 C) to be 0.376 mmol g-1, which is in agreement with the Al content of the zeolite (0.35 mmol g-1). Thermograms obtained from the TPD experiments show one desorption maximum at around 300 360 C. Similar results have been reported in literature [1]. A microkinetic model was formulated to describe the zeolite particles and the TPD conditions. Intraparticle mass transfer was taken into account as activated and non-activated diffusion. Adsorption was assumed to be non-activated, and the reactor cell was assumed gradientless. Three different adsorption models were tested: (1) one Langmuir-type adsorption site, (2) two Langmuir-type sites, and (3) one adsorption site with surface coverage-dependent desorption activation energy (Edes()). Optimization of the model parameters was carried out using the difference between simulated and experimental data as the objective function to minimize with the Nelder-Mead simplex algorithm. To be able to compare the models, also the effect of intraparticle mass transfer must be addressed adequately. Parameter estimates obtained for experimental data with adsorption at 100 C were also used in simulation to evaluate their suitability to experiments with adsorption at 200 C. The results from different models and obtained parameter estimates will be reported and discussed. In this case study, several adsorption temperatures had to be used to obtain good parameter estimates for sorption kinetics. Due to using vacuum TPD, reactor cell and interparticle mass transfer models are not as important as in atmospheric TPD modeling. The focus of this study is in modeling sorption kinetics and intraparticle mass transfer, both of these describing the zeolite instead of the experimental conditions. References Tago, T., Okubo, Y., Mukai, S., Tanaka, T., Masuda, T., Simultaneous characterization of acidic [1] and basic properties of solid catalysts by a new TPD method and their correlation to reaction rates, Appl. Catal., A 290 54 (2005).

O29 Structural environments for surface sites in boron- and phosphorous-modified alumina catalysts from single- and double-resonance 1 H, 11B, 31P, and 27Al MAS NMR experiments
Michael Ryan Hansen1,2, Sren Srensen1, Hans J. Jakobsen1, and Jrgen Skibsted1 1 Instrument Centre for Solid-State NMR Spectroscopy and Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, 8000 C Aarhus, Denmark. 2Present Address: Max-Planck-Institute for Polymer Research, D-55021 Mainz, Germany. E-mail: jskib@chem.au.dk Abstract The catalytic properties of hydrotreating catalysts depend strongly on the surface structure and acidity of the support material. As a consequence, improved catalytic materials can be obtained using modifier elements such as silica, phosphates, boria, fluorides and chlorides, which affect either the solubility and stability of the transition-metal species in the impreg-nation process or improve the thermal stability of the alumina support. The present work focuses on boron- and phosphorous-modified alumina supports, utilizing a range of solid-state MAS NMR techniques to characterize the bonding of the modifiers to the alumina surface, the connectivities of different phosphate and borate species, and the interaction with hydroxyl groups and absorbed water on the alumina support. For example, 11B{27Al} REDOR and TRAPDOR NMR experiments reveal the types of borate species anchored to the surface via BOAl bonds while 11B homonuclear correlation experiments give information about BO4BO3 connectivities and thereby a network of these units on the surface [1]. For phosphorus-modified alumina, similar information about the phosphate species and their connectivities may be achieved from 31P 27Al REDOR-type sequences as well as 31P MAS correlation experiments. The present work also investigates the hydroxyl groups and water molecules adsorbed on the alumina surface and on the borate and phosphate species. The dynamics of the water molecules and their removal from the modified surfaces by heat-treatment are studied by 1H11B/27Al/31P double-resonance experiments [2]. Furthermore, very high-speed 1H MAS NMR is used to reduce homonuclear dipolar interactions, thereby providing chemical shift information about different 1H surface species on the modified P- and B-Al2O3 samples. Finally, special attention is paid to the penta-coordinated AlO5 sites, formed by heat-treatment of the alumina at rather high temperatures, since these sites may play an important role in the anchoring of the transition metals to the alumina surface.

Figure 1: Schematic drawing of the hydrous surface structure for the alumina-boria catalyst, summarizing the information derived from the MAS NMR experiments in the present study. [1] [2] M. R. Hansen, H. J. Jakobsen, J. Skibsted, J. Phys. Chem. C 112, 7210 (2008). M. R. Hansen, H. J. Jakobsen, J. Skibsted, J. Phys. Chem. C 113, 2475 (2009).

O30 Advances in transmission electron microscopy for catalysis

Alfons M. Molenbroek, Stig Helveg Haldor Topse A/S, Nymllevej 55, DK-2800 Lyngby, Denmark E-mail: am@topsoe.dk Abstract Improvements in the understanding of catalysts and catalytic reactions strongly correlate with new developments in characterization techniques. Especially, the advancement in high-gas-pressure- and high-temperature- in situ probes to obtain structural and chemical information down to the atomic scale has contributed to new insights in the dynamic nanostructure of heterogeneous catalysts under operating conditions [1]. Here, the application of two recent advances in transmission electron microscopy (TEM) for heterogeneous catalysis will be discussed. The first advancement is concerned with high-resolution TEM (HRTEM) imaging of the shape and structure of industrial-style prepared graphite-supported MoS2 nanocatalysts for hydrotreating reactions [2]. Previously, it was difficult to obtain atomic-resolved TEM images of the MoS2 nanocatalysts due to insufficient image contrast or resolution. However, the introduction of aberration-corrected HRTEM has now made it possible to obtain atomically resolved images with a sensitivity at the single-atom level (see figure). The second advancement is the introduction of MEMS (microelectromechanical systems) nanoreactors for in situ HRTEM of nanostructured materials during exposure to reactive gases at ambient pressure and high temperature. The pressure exceeds that of existing HRTEM systems by a factor of hundred and is at a level of relevance for catalyst testing. The reactor integrates a micro-meter sized gas-flow channel with a microheater and with an array of electron-transparent windows of silicon nitride. The nanoreactor performance is demonstrated on a methanol-synthesis catalyst by the observation of the formation of Cu particles on ZnO support with atomic-scale resolution [3,4].

Figure: Atomic arrangement of industrial-style MoS2 catalysts observed by single-atom-sensitive TEM. References [1] A. Stierle and A.M. Molenbroek, Guest editors, MRS Bulletin, 32-12, 1001 (2007) [2] C. Kisielowski, Q.M. Ramasse, L.P. Hansen, M. Brorson, A.Carlsson, A.M. Molenbroek, H. Topse and S. Helveg, Angewandte Chemie, published on line, March 15 (2010) [3] J.F. Creemer, S. Helveg, G.H. Hoveling, S. Ullmann, A.M. Molenbroek, P.M. Sarro, H.W. Zandbergen, Ultramicroscopy 108, 993-998 (2008) [4] J. F. Creemer, S. Helveg, P.J. Kooyman, A.M. Molenbroek, H.W. Zandbergen, and P.M. Sarro, Journal of Microelectromechanical Systems, IEEE Early Access, Issue 99, 1-11(2010)

O31 Environmental TEM of the Dynamics of Catalyst Particles

Thomas W. Hansen1, Jakob B. Wagner1, Linus D. L. Duchstein1, Filippo Cavalca1 and Rafal E. DuninBorkowski1 1 Center for Electron Nanoscopy, Tech. University of Denmark, DK-2800, Lyngby, Denmark E-mail: twh@cen.dtu.dk Abstract Transmission electron microscopy (TEM) is used extensively in catalysis research [1]. Recent developments in instrumentation include monochromation of the electron source and aberration correction of both the condenser and the objective lens system. These developments are now also being introduced into the environmental TEM (ETEM). The improved spatial resolution and interpretability resulting from the implementation of aberration correctors are beneficial for imaging the surface structures and dynamics of catalyst nanoparticles. Whereas conventional high-vacuum TEM provides important information about morphologies and atomic arrangements, ETEM capability allows materials such as catalysts to be investigated under gas exposure at elevated temperature. In this way, catalytic processes can be followed in a simulated working environment. Furthermore, phenomena such as sintering and growth can be observed dynamically [2]. In order to initiate a systematic study of the dynamics of nanoparticles, we exposed a model system of gold nanoparticles on boron nitride to 1.3 mbar of H2 at 410C in an image CS corrected FEI Titan 80300 ETEM. Image sequences were acquired at 2 frames/s. Mobility of the particles was visible, while maintaining lattice resolution of both the BN and the Au. Some particles remained immobile during observation, while others moved on the support (see figure) and sintered by migration and coalescence. Other particles were observed to shrink in size and disappear as neighbouring particles grew by Ostwald ripening. Fundamental insight into activation energies and energy barriers for sintering processes will be studied by quantifying these observations.
a) c) c) d)

2nm

t=0s

t=37.2s

t=104.2s

t=113.0s

Frames extracted from an image sequence acquired in an environmental TEM in 1.3 mbar of H2 gas at 410C. Arrows indicate the positions of coalescence events and Ostwald ripening. The times are relative to the first frame shown. References [1] A. K. Datye, J. Catal. 216, 144 (2003). P. Wynblatt and N. A. Gjostein, Prog. Solid State Chem. 9, 21 (1975). [2]

O32 Identical locations transmission electron microscopy study of Pt/C catalyst corrosion under oxygen reduction reaction conditions
Christian F. Elkjr1, Francisco J. Prez-Alonso1, Billie L. Abrams1, Ifan E.L. Stephens1, Ib Chorkendorff1 1 Center for Individual Nanoparticle Functionality, Department of Physics, Building 312, Technical University of Denmark, DK-2800 Lyngby, Denmark E-mail: Francisco.Perez@fysik.dtu.dk Proton exchange membrane fuel cells (PEMFCs) could possibly play a major role in a future carbon-free society, with their ability to convert chemically stored energy into electricity. Arguably the most significant obstacle preventing the widespread utilisation of PEMFCs is their low efficiency and high cost. The majority of the inefficiencies can be traced back to the performance of the Pt/C electrocatalysts at their cathodes, which drive the oxygen reduction reaction (ORR). Most research efforts in relation to these catalysts have focused on the improvement of their activity. However, fewer studies have concentrated on their durability, despite the critical importance of catalyst stability for PEMFC applications. Fundamental investigations are needed to improve our understanding of the degradation mechanism(s) of Pt/C electrocatalysts during the ORR. Recent studies [1, 2] demonstrated the use of identical location transmission electron microscopy (ILTEM) to examine identical locations of a sample before and after electrochemical reactions. The current investigation aims to further elucidate the corrosion mechanism(s) of Pt/C electrocatalysts at a PEMFC cathode. The effect of fuel cell load cycling was simulated by cycling the potential between 0.6 and 1.2 V at different scan rates. Whereas in previous studies a Pt/C loaded TEM grid was connected in parallel to another working electrode [1, 2], here the TEM grid was the only working electrode. With this configuration, it was possible to directly observe the electrochemical response of the catalysts that were characterised using IL-TEM. Figure 1 shows an example TEM of Pt/C electrocatalyst before (left) and after (right) 3000 cycles between 0.6 V and 1.2 V [RHE], using a scan rate of 200 mVs-1. A significant decrease in surface area and number of nanoparticles was observed after ORR cycling. The effects of ORR cycling under various conditions along with other treatments on catalyst stability will be discussed.

Figure 1: IL-TEM of Pt/C electrocatalyst before (left) and after (right) ORR cycling (between 0.6 and 1.2 V [RHE], 3000 cycles, Scan rate=200 mVs-1) References [1] K. J. J. Mayrhofer, S. J. Ashton, J. C. Meier, G. K.H, Wiberg, M. Hanzlik, M. Arenz, J. Power Sources, 185, 734 (2008). [2] K. J. J. Mayrhofer, J. C. Meier, S. J. Ashton, G. K.H, Wiberg, F. Kraus, M. Hanzlik, M. Arenz, Electrochem. Comm. 10, 1144 (2008).

O33 Electron microscopy characterization of materials relevant to catalysis

Lars F Lundegaard1, Stig Helveg1 1 Haldor Topse A/S, Nymllevej 55, 2800 Kgs. Lyngby, DK E-mail: lalf@topsoe.dk Abstract Due to the complex structure of heterogeneous catalysts, a detailed structural characterization at all length scales right down to the atomic scale is of crucial importance to improve the understanding of the catalysts structure-performance relationship. In the intermediate range (down to a few nanometers) we are usually interested in three-dimensional structural insight into pore structures and catalyst particle shapes and sizes as well as the particle distribution on the support. For structural information at these length scales it is beneficial to apply x-ray and electron tomography techniques [1]. To get information at the atomic structure length scales, high-resolution transmission electron microscopy offers unique possibilities. But in many cases information like phase identification, lattice parameters, symmetry and the relationship between crystallographic axis and crystal morphology is not easily obtained from HRTEM. We have therefore developed quantitative electron diffraction techniques which work well for both nano-crystalline powders and single crystals (See figure1). I will present these electron microscopy techniques illustrated with a range of problems and materials.

Figure 1 : TEM micrograph of a zeolite single crystal supported by a lazy carbon film coated with gold. The insert is showing the selected area diffraction pattern. Bragg spots are from the zeolite single crystal and powder rings are from the gold particles used as internal diffraction standard. References [1] Laursen, A.B. et al., Angew. Chem. Int. Ed. (2010) Accepted.

O34 In situ studies of Pd and Rh model catalysts

E. Lundgrena,*, J. Gustafsona, S. Blomberga, R. Westerstrma, J. N. Andersena, O. Balmesb, R. Van Rijnbc, J. W. M. Frenkenc, H. Bluhmd, M. Messinge, K. Depperte a Division of Synchrotron Radiation Research, Lund University, Sweden. b ESRF, Grenoble, France. c Leiden University, Leiden, the Netherlands d ALS, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. e Division of Solid State Physics,, Lund University, Sweden. *E-mail: edvin.lundgren@sljus.lu.se Abstract For many years there has been little overlap between the catalytic industry and surface science and surface chemistry, largely because of the simplified catalytic model systems and low pressures used in fundamental studies. However, during the last decade a number of new experimental techniques have emerged [1] allowing for atomic scale studies at conditions closer to real catalysts at work. Thus it has been reported that the formation of compounds between the active catalyst and the reactant gas such as oxides [2-6] and carbides [7] may occur, which strongly affect the catalytic properties. Although some of these reports have been disputed [8] it becomes increasingly clear that the simple picture of adsorption and reaction of atoms on an unmodified substrate is inadequate in many cases, even for the noble metals of the Pt group. In this contribution we present in situ studies of the oxidation and CO oxidation over Rh and Pd model catalysts using High Pressure X-ray Photoelectron Spectroscopy (HPXPS) and in situ Surface X-Ray Diffraction (SXRD). The model catalyst used has been either single crystals or size selected aerosol particles with sizes of 15, 20 or 35 nm in diameter deposited onto either SiOx or Al2O3 substrates. We show that the oxidation properties of single crystals and particles are similar, and that in oxygen rich conditions the presence of a thin oxide promotes the CO2 production. While CO is observed to adsorb on Pd and Rh single crystals as well as on Rh particles in oxygen poor conditions and low CO2 production, a Pd carbide is formed in the Pd nanoparticles. References [1] A. Stierle and A. Moelenbroek, Special Issue of MRS Bull. 32 (2007) 1000 [2] B. L. M. Hendriksen and J. W. M. Frenken, Phys. Rev. Lett. 89, 046101 (2002). [3] J. Gustafson et. al., Phys. Rev. B 78, 045423 (2008). [4] R. Westerstrm et. al., J. Phys. Cond. Matter 20, 184018 (2008). [5] M. A. Newton et. al., Chem. Eur. J., 12 1975 (2006). [6] J. Rogal, K. Reuter, and M. Scheffler Phys. Rev. Lett. 98, 046101 (2007). [7] D. Teschner et al., Science 320 (2008) 86. [8] M. S. Chen et. al., Surf. Sci. 601, 5326 (2007).

O35 Making EXAFS surface sensitive? Red-ox cycles on Rh/Al2O3

Davide Ferri1, M. Santhosh Kumar1, Paul Hug1, Anke Weidenkaff1, Mark A. Newton2 1 Empa, Lab. for Solid State Chemistry and Catalysis, CH-8600 Dbendorf, Switzerland 2 ESRF, F-38000 Grenoble, France E-mail: davide.ferri@empa.ch Abstract Automotive catalysts operate under severe conditions of temperature and atmosphere. They experience fast transients and periodic reaction conditions that are challenging to reproduce for mechanistic studies. Improved data evaluation is required to separate the contribution of intermediate species from that of the dominating spectator species. This can be achieved by a demodulation technique [1], that has been applied to energy dispersive -EXAFS, a typical bulk technique in an effort to capture the behaviour of noble metals at ca 4Hz, thus under conditions relevant to automotive catalysis. The time-resolved EDEXAFS spectra collected during a modulation experiment (CO vs. NO) display only subtle changes in the absorption spectra. It is obvious from the spectra of Rh/Al2O3 that Rh remains essentially reduced throughout the experiment. The demodulation algorithm generates a set of phase-resolved spectra in which the absorption jump is filtered out as well as all other features responding at a different frequency than that of the external stimulation. This processing considerably reduces the noise in the spectra. Small features in the EXAFS region can be then clearly resolved. From the demodulation envelopes the temporal behavior of the structural changes is precisely assessed from the averaged time-resolved spectra. The whole approach provides surface sensitivity to the EXAFS method: the data reveal that during the CO-NO pulses Rh periodically changes from reduced to partially oxidised. The temporal response of various signals also reveals that the observed subtle changes occur at different rates thus uncovering detailed structural-dynamic behaviour of the system. Oxidation is slow compared to reduction and consists in the rapid formation of a thin oxidic layer followed by its slower growth. All this information is coupled to the synchronous DRIFT and MS data collected synchronously with the ED-EXAFS data to obtain mechanistic information on the process [2].

Figure 1: Averaged time-resolved ED-EXAFS spectra of 2 wt% Rh/Al2O3 obtained at the Rh K-edge from 5% CO vs. 5% NO cycles at 300C; corresponding phase-resolved spectra; temporal response of selected signals.

References [1] D. Baurecht, U.P. Fringeli, Rev. Sci. Instr. 72, 3782 (2001). [2] D. Ferri, M. Santhosh Kumar, R. Wirz, A. Eyssler, O. Korsak, P. Hug, A. Weidenkaff, M.A. Newton, PCCP, in press.

O36 High throughput experimentation as an efficient tool for the testing of hydroprocessing catalysts
Josef Find1, Philipp Hauck1, Jochen Berg1, Michael Paul1 1 hte Aktiengesellschaft - Kurpfalzring 104, 69123 Heidelberg, Germany E-mail: Philipp.Hauck@hte-company.de Abstract Increasing global demand for fuels, the tightening of environmental regulations and the optimization of refineries has led to an increasing demand for catalyst testing capacity. High throughput catalyst testing is a time-efficient approach for meeting this demand, however, in the past the increase in testing throughput was subsequently accompanied by a loss of data quality. The demand for hydroprocessing and the testing of hydroprocessing catalysts has been growing steadily over the past years and this seems unlikely to decrease in the future. Over the last couple of years hte has developed parallel testing reactor systems for testing these catalysts under a wide range of process conditions in order to meet this demand. The latest development is capable of processing VGO, heavy VGO and bio-oil under industrially relevant conditions. Temperatures of up to 450C can be achieved routinely, as well as pressures from 20 up to 170 bar. A challenging example for the parallel testing of hydroprocessing catalysts is hydrocracking. The products of this process depend strongly on the reaction conditions (temperature, pressure, catalyst activity). These products range from ethane, LPG to heavier hydrocarbons comprising mostly isoparaffins. Closing the total carbon mass balance covering gas and liquid products, under demanding reaction conditions is one of the latest major achievements for high throughput reactor systems. The results that will be presented will show the effectiveness of parallel testing technology and the data quality standard in a reactor-to-reactor and run-to-run comparison for hydrodesulphurization and hydrocracking processes over several months feeding diesel, VGO, heavy VGO and bio-oil. To prove the value of the achieved data, the experimental results will be compared to pilot plant data. The latest developments in the field of high throughput reactor technology for refinery applications will also be shown, including parallel catalyst testing technology in a sub-pilot scale with higher catalyst volumes.

O37 Probing the atomic-scale details of molecular adsorption on MoS2 and CoMoS nanoclusters in hydrotreating catalysis
Jeppe V. Lauritsen1, Anders K. Tuxen1, Henrik Gbel1, Henrik Topse2, Flemming Besenbacher1 1 Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Denmark 2 Haldor Topse A/S, Lyngby, Denmark Email: jvang@inano.au.dk Abstract A distinct advantage of the Scanning Tunneling Microscope (STM) is its capability to resolve the realspace, atomic-scale structure of nanoclusters. This opens the unique opportunity to experimentally address the edge structure of single-layer MoS2 nanoclusters, which contain the active sites for hydrotreating reactions. In my presentation, I will demonstrate how we have taken advantage of the STM to resolve molecular adsorption on the edges of MoS2 and a range of promoted CoMoS-type structures synthesized on a gold model substrate. In general, the STM studies reveal that both unpromoted MoS2 and CoMoS nanoclusters adopt edge structures that are significantly electronically and geometrically reconstructed compared to bulk-truncated forms. To elucidate the role of the particular CoMoS and MoS2 edge structures in hydrotreating reaction, we have investigated the chemical bonding to a number of relevant S- and N-containing probe molecules. The new findings shed detailed light on the role of the modified electronic structure and undercoordinated sites and resolve the configuration in which the molecules preferably interact at these sites. In particular, we have been able to address the atomic-scale origin of inhibition effects caused by N-containing molecules, which are directly seen in STM images to selectively block the active sites on the cluster edges.

Figure: Atom-resolved STM images of a small MoS2 nanocluster showing formation of S vacancies and subsequent adsorption of dibenzothiophene (DBT) on corner sites

Furthermore, we have also thoroughly elucidated the fundamental adsorption selectivity of MoS2 nanoclusters towards the group of refractory dibenzothiophenes (DBT). Interestingly, we report a pronounced size-dependent chemical affinity for direct adsorption of DBT, which is induced by structural edge changes also observed in STM studies of the smallest MoS2 structures [1]. The atomicscale observations of molecular adsorption on both unpromoted and promoted MoS2 model catalysts correlate well with observed activity parameters for the technical catalyst, and the new detailed atomic scale insight suggests that improvements may be realized by an enhanced control of the nanocluster. References [1] Lauritsen J V, Kibsgaard J, Helveg S, Topse H, Clausen B S and Besenbacher F 2007 Nature Nanotechnology 2 53-8

O38 Reactivity of ruthenium steps

Kenneth Nielsen1, Yann Tison1, Sren B. Vendelbo1, Duncan Mowbray2, Lone Bech1, Ib Chorkendorff1, Jane H. Nielsen1,* 1 Center for Individual Nanoparticle Functionality (CINF), Department of Physics at DTU 2 Center for Atomic-scale Materials Design (CAMD), Department of Physics at DTU *E-mail: jane@fysik.dtu.dk Abstract CO dissociation is relevant for several industrial processes, such as methanation and the Fischer-Tropsch synthesis. To obtain parameters for improving catalysts, it is important to identify the nature of the active site. On ruthenium, DFT calculations and desorption experiments showed that step sites play an integral role for this reaction [1]. With the purpose of illuminating the role of step sites further, we studied CO dissociation on a Ru(0 1 54) single crystal as a model system under UHV and imaged the surfaces with STM. This crystal presents a well defined density of steps (~4% of the atoms in the surface are located at steps), which alternate between two different atomic configurations, see figure 1a. After exposing the crystal to large pressures of CO (10-5 torr) at 550 K, STM images first show a roughening of every other step, see figure 1c, as compared to the clean surface, figure 1b. For even higher doses, we observe that the steps straighten out again [2], see figure 1d. This corroborates previous results presented in ref. [1]. In this study, the peak in CO TPD experiments previously assigned to dissociated CO desorbed from the steps by Zubkov and co-workers [3], was quantified as a function of the same pre-treatment CO dose magnitude as in the STM experiments. For increasing doses, the amount of step-desorbed CO was found to first increase forming a maximum and then drop down to a stable level [1]. Higher resolution STM images reveal step decorations. On top of the steps, a structure with a periodicity corresponding to the double of the atomic spacing in Ru is seen [2]. This could correspond to oxygen from the dissociated CO, resulting in images similar to those previously observed after NO dissociation on the steps for Ru(001) [4].

Figure 1: a) A model of the Ru(0 1 54) single crystal. The steps alternate between A5 and B5 configuration. b) STM of the clean crystal. All steps are clean and straight c) After 7 min. of CO dose, 10-5 Torr at 550 K. Every other step has decorations and looks rougher, while the other half are straight. d) After 14 min. of CO dose, same conditions. Less step decoration is seen.

References [1] S.B. Vendelbo et al. Topics in catalysis. Accepted 2009 [2] Y. Tison et al. In preparation. [3] T. Zubkov et al. Chem. Phys. Lett. 362, 181 (2002) [4] T. Zambelli et al. Science 273, 1688-1690 (1996)

O39

O40 CO methanation over Ru-Al2O3 catalysts: effects of chloride doping on reaction activity and selectivity
Djinovi Petar1, Galletti Camilla2, Specchia Stefania2, Specchia Vito2 1 National Institute of Chemistry, Ljubljana, Slovenia 2 Department of Materials Science and Chemical Engineering, Politecnico di Torino, Italy E-mail: camilla.galletti@polito.it Abstract CO methanation is a feasible catalytic process aimed to obtain essentially CO free hydrogen rich gas for further use in various processes, where absence of CO is a critical issue, i.e. PEM fuel cells [1] or ammonia synthesis [2]. The purpose of this work was to investigate the performance of Ru-based catalysts on alumina carrier for CO methanation and to establish the role of the Ru precursors, the doping effect of chloride and the Ru loading on efficient CO removal at low temperatures with simultaneous reduction/inhibition of CO2 methanation. The solution combustion synthesis technique was used to prepare the Al2O3 carrier [3], which was calcined in still air at 650 C for 2 h. Ruthenium was deposited by impregnation with aqueous solution of both RuCl3 and Ru(NO)(NO3)3 to yield Ru loads of 1, 3 and 5 wt. %. Chloride was added to Ru(NO)(NO3)3 prepared catalysts via subsequent impregnation with aqueous solution of NH4Cl (yielding a molar Ru:Cl ratio of 1, 3 and 9), followed by calcination in still air at 350 C for 2 h. The obtained catalysts were characterized by XRD, BET, FESEM-EDX, H2-TPR and XPS techniques. The methanation tests were carried out between 150 and 450 C, feeding a gas stream of 0.5 % CO, 18 % CO2, 40 % H2 and N2 as balance (total flow-rate of 100 Nml min-1). A critical parameter in assessing the catalysts as selective CO methanation ones was the operating temperature range T characterized by simultaneous complete CO conversion (CO = 1) and ratio R of formed CH4 to consumed CO below 1.5 (R 1.5). Ru-Al_Cl catalysts enabled wide T values (see first column, in Table 1), whereas T resulted practically equal to zero with Ru-Al_NO3 catalysts (prepared from Ru(NO)(NO3)3, see second column in Table 1), showing the presence of residual chlorine as a key factor for high catalyst selectivity. In fact, the addition of chlorine through NH4Cl solution impregnation (molar Ru:Cl of 1, 3 and 9) to fresh 1 and 3% Ru-Al_NO3 catalysts tremendously improved their selectivity toward CO methanation. In particular, with 3% Ru-Al_NO3_Cl catalysts, a significant improvement in their activity was also observed (see third column in Table 1), with a further increase in T, compared to the values obtained with Ru-Al_Cl catalysts.
Table 1: Operating T with simultaneous CO = 1 and R 1.5 for the Ru-Al2O3 catalysts.

Catalyst 1% RuAl_Cl 3% RuAl_Cl 5% RuAl_Cl

T [C] 221 264 = 43 211 241 = 30 211 263 = 42

Catalyst 1% RuAl_NO3 3% RuAl_NO3 5% RuAl_NO3

T [C] ~0 ~0 ~0

Catalyst 3% RuAl_NO3_1 3% RuAl_NO3_3 3% RuAl_NO3_9

T [C] 189 230 = 41 190 249 = 59 188 246 = 58

References [1] M.B.I. Choudhury, S. Ahmed, M.A. Shalabi, T. Inui, Appl. Catal. A: Gen. 314, 47 (2006). [2] I. Chorkendorff, H. Niemantsverdriet, WileyVCH, Weinheim, ISBN 978-3-527-31672-4, 2007. [3] C. Galletti, S. Fiorot, S. Specchia, G. Saracco, V. Specchia, Topics Catal. 45, 1 (2007).

O41 Influence of phosphorous aging on diesel oxidation catalysts

Alexander Winkler1, Davide Ferri2, M. Santhosh Kumar2, Myriam Aguirre2 1 Empa, Internal Combustion Engines Laboratory, Duebendorf, Switzerland 2 Empa, Laboratory for Solid State Chemistry and Catalysis, Duebendorf, Switzerland E-mail: alexander.winkler@empa.ch Abstract Increasingly stringent emission regulations for the automotive sector (upcoming Euro 6) in combination with high durability demands for the exhaust aftertreatment system requires detailed knowledge of the catalyst aging phenomena. Whereas thermal aging occurs due to high temperature induced sintering, chemical aging results from combustion products of motor oil based additives. Analysis of an engine aged, commercially available diesel oxidation catalyst (DOC) shows that the chemical aging compounds primarily accumulate on the washcoat surface in the inlet area of the DOC. Among all detected compounds phosphorous was the only one which also accumulated in the washcoat.

Figure 1: HR-TEM images of platinum particles from the inlet (a) and outlet (b) area of an aged diesel oxidation catalyst (DOC) as well as from a new DOC (c). Phosphorous in the washcoat seems to influence the morphology of the catalytically active platinum particles upon thermal induced sintering. HR-TEM images of platinum particles of the aged DOC inlet area (Figure 1a) show a spherical morphology, whereas in the absence of phosphorous (aged DOC outlet area, Figure 1b) the structure of the sintered platinum particles is mostly polyhedral. Additionally, the average particle size increases from the inlet to the outlet area [1]. The structure of the platinum particles and the presence of phosphorous selectively influence the NO oxidation activity. Whereas aged DOC samples from the inlet and outlet area showed comparable activity for CO and HC conversion, the NO oxidation activity to NO2 was selectively lower for the inlet area. Phosphorous reduces the amount of NO2 generated by the DOC which again limits the efficiency of subsequent exhaust aftertreatment devices. Results on a powder Pt/Al2O3 catalyst artificially aged with phosphorous will be presented which confirm that the phenomenon is general and is additionally driven by the reacting gas composition. References [1] A. Winkler, D: Ferri, M. Aguirre, Appl. Catal. B: Environmental 93, 177 (2009).

O42 Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
Ifan E.L. Stephens1, Jeffrey Greeley2,3, Alexander S. Bondarenko1, Heine A. Hansen2,4, Federico Calle Vallejo2, Tobias Johansson1, Thomas F. Jaramillo1,5, Jan Rossmeisl2, Ib Chorkendorff1,*, Jens K. Nrskov2,* 1 CINF, Technical University of Denmark, (DTU), Lyngby, Denmark. 2 CAMD, Technical University of Denmark, (DTU), Lyngby, Denmark. 3 Current address: Argonne National Laboratory, IL, USA. 4 Current address: Northwestern University, IL, USA. 5 Current address: Stanford University, CA, USA. *E-mail: ibchork@fysik.dtu.dk, norskov@fysik.dtu.dk
The development of low temperature polymer electrolyte membrane fuel cells (PEMFCs) is severely hampered by the fact that the oxygen reduction reaction (ORR) is slow, even using platinum as a catalyst. Platinum is expensive and scarce, and it has been suggested that for PEMFCs to become viable, Pt based catalysts would need to show a stable catalytic activity of at least 2-4 times that of pure Pt [1]. Several Pt alloys, including late transition metals such as Ni, Co, Cr, and Cu, are considerably more active than Pt and have been studied intensively [1-3]. Here we present a new set of platinum compounds. The catalysts consist of Pd or Pt alloyed with early transition metals such as Sc or Y. They were identified using density functional theory calculations as being the most stable Pt- and Pd-based binary alloys with oxygen reduction catalytic activity likely to be better than Pt. Bulk polycrystalline electrodes of Pt3Y and Pt3Sc were characterized electrochemically in a rotating disc assembly in 0.1 M HClO4. Electrochemical measurements show that the activity of polycrystalline Pt3Sc and Pt3Y electrodes is enhanced relative to pure Pt by a factor of 1.51.8 and 610, respectively, in the potential range 0.90.87 V [4]. We have now extended the scope of our theoretical and experimental studies to investigate other alloys of Pt and early transition metals, including PtZrx, PtHfx and PtLax. References [1] H.A. Gasteiger, S.S. Kocha, B. Somappli and F.T. Wagner, Appl. Catal. B-Environ., 56, 9 (2005). [2] V. Stamenkovic et al. Angew. Chem. Int. Ed. 45 2897 (2006) . [3] S. Koh and P. Strasser,. J. Amer. Chem. Soc. 129, 12624 (2007). [4] J. Greeley, I.E.L. Stephens, A.S. Bondarenko, T.P. Johansson, H.A. Hansen, T.F. Jaramillo, J. Rossmeisl, I. Chorkendorff and J.K. Nrskov, Nature Chemistry, 1 552 (2009).

O43 Deactivation of ion exchange catalysts by acetonitrile and methylamine

Jordi-Hug Badia1, Rafael Gonzlez1, Carles Fit1, Fidel Cunill1, Klaus-Dieter Topp2 1 Dept.Chemical Engineering, University of Barcelona (Spain) 2 Rohm and Haas Europe Services APS Deutsche Zweigniederlassung, Frankfurt (Germany) a wholly owned company of The Dow Chemical Company E-mail: fite@ub.edu Abstract Acetonitrile (ACN) and methylamine (MMA) deactivate acidic ion exchange resins used as catalysts for etherification reactions. Effect of ACN and MMA has been evaluated in the ETBE synthesis reaction in the liquid phase, as they could be present in the industrial C4-cut feed used as reactant. Experiments were carried out in a continuous isothermal tubular packed bed microreactor (15 cm length, 7.0 mm i.d.), at 40C80C and in the liquid phase (pressure: 1.6 MPa). Reactor feed was a mixture of an industrial FCC C4-cut stream (22.9%-wt isobutene) and absolute ethanol, in a molar ratio alcohol to isobutene equal to 1.1. As the catalyst, AmberlystTM 35WET and AmberlystTM 15WET were used, diluted with inert glass. Catalyst beads size and reactants flow rate were selected to avoid internal and external mass transfer resistances, respectively. Small amounts of catalyst were used to obtain low conversion levels, so the reactor behaved differentially and the deactivating effect can be considered uniform along the bed. The deactivating agent was fed with the ethanol stream in concentrations that were chosen to monitor a significant deactivating effect during the experiments, that lasted up to five hours (ACN: up to 5000 ppm, MMA: up to 430 ppm). Deactivation progress was evaluated by comparing the observed reaction rate during the experiments and the reaction rate previously measured in absence of the deactivating agent. The observed results showed a similar activity decrease for both AmberlystTM 35WET and AmberlystTM 15WET, but somehow different with respect to ACN and MMA. The global behaviour is shown in Figure 1, where zero time is the instant when the deactivating agent begins to enter to the reactor: Zone 0: at low temperature, constant activity, and, at high temperature, slight activity decrease attributed to secondary reactions of the C4-cut or impurities. Zone 1: period significantly longer than the reactor residence time in which the deactivating agent would interact with the resin, making accessible active Figure 1: Deactivation progress by ACN and centres that were not accessible initially in the MMA absence of the deactivating agent. This would compensate the lost of activity by ACN or MMA. The slope of this trend is positive in the case of ACN at 40C and low concentrations. Zone 2: Exponential-like decrease of activity. With ACN, it finishes to a practically constant positive value (slope at very long time is the same as in Zone 0, compatible with the remaining deactivation by C4-cut components). With MMA, it drops suddenly to zero. The transition between Zone 1 and Zone 2 is sharp for ACN and smooth for MMA. Globally, deactivation effect is much stronger for MMA than for ACN. Reaction rates are higher for AmberlystTM 35WET than for AmberlystTM 15WET under the same conditions.

O44 Glycerol etherification to dimers using basic and acidic catalysts

Andreas Martin, Manfred Richter Leibniz Institute for Catalysis, Albert-Einstein-Str. 29a, D-18059 Rostock, Germany E-mail: andreas.martin@catalysis.de Abstract Etherification is a promising way for valorization of glycerol. Besides conversion to fuel blending components (e.g. tert.-butyl ethers [1]), glycerol etherification to di- and polyglycerols yields attractive products required for manufacturing of biodegradable surfactants, lubricants, cosmetics, food additives and others. Earth alkaline oxides [2,3] or alkaline modified zeolites and mesoporous materials [4] are reported to be promising solid catalysts for glycerol etherification to diglycerol. A theoretical study on the role of surface basicity and Lewis acidity is described in [3]. The current contribution will give an overview on the base- and acid-catalyzed reaction pathways including application of heterogeneous and homogeneous catalysts. Recently, we have shown [5] that the etherification reaction using Na and Cs modified zeolites X, Y and Beta can favorably be accomplished at 260 C under atmospheric pressure. Activity (glycerol conversion after 8 h reaction time) was found to be highest on CsX, with 63 % glycerol conversion and selectivity to linear diglycerol of ca. 80 %. However, XRD and SEM analysis of spent catalysts proved that CsX zeolites suffered a structural collapse during reaction with release of Cs into solution (as confirmed by XRF). This inspired us to look for the role of alkali metal salts that can be considered as homogenous catalysts because of their facile solubility in glycerol. Whereas the influence of the cations was not significant, the conversion of glycerol decreased using CsOH, CH3COOCs and CsNO3. The highest conversion was observed for CsOH, one of most powerful base in aqueous solution. Alternatively, an acidic reaction route has been investigated, to avoid the drawback of separating the desired products from solid and dissolved catalyst components. The acid-catalyzed glycerol etherification was carried out in a tube reactor under reflux vacuum conditions at ca. 150-180 C [6,7] using a super-acidic polymer resin as catalyst. The glycerol had only short contact time with the resin catalyst where the etherification proceeded in a liquid film running across the catalyst foil. The di/polyglycerol mixture was accumulated at the bottom of the reactor construction. This reaction technology allowed maintaining high selectivity of digylcerol at nearly complete glycerol conversion. References [1] A. Behr, L. Obendorf, Chem. Ing. Techn. 73 (2001) 1463. [2] A.M. Ruppert, B.M. Weckhuysen, J.D. Meeldijk, B.W.M. Kuipers, B.H. Ern, Chem. Eur. J. 14 (2008) 2016. [3] M. Calatayud, A.M. Ruppert, B.M. Weckhuysen, Chem. Eur. J. 15 (2009) 10864. [4] F. Jrme, Y. Pouilloux, J. Barrault, ChemSusChem 1 (2008) 586. [5] Y.K. Krisnandi, R. Eckelt, M. Schneider, A. Martin, M. Richter, ChemSusChem 1 (2008) 835. [6] M. Richter, R. Eckelt Y.K. Krisnandi, A. Martin, Chem. Ing. Techn. 80 (2008) 1573. [7] Patent DE 10 2007 042 381 B3, LIKAT.

O45 In-situ FT-IR mechanistic investigations of the zeolite catalyzed methylation of benzene with methanol: H-ZSM-5 vs H-beta.
Melina Visur1, Stian Svelle1, Unni Olsbye1, Saepurahman2, Morten Bjrgen2 1 inGAP center of research based innovation/Dept. of Chemistry, University of Oslo, Norway 2 Dept. of Chemistry, Norwegian University of Science and Technology, Trondheim, Norway E-mail: stian.svelle@kjemi.uio.no Abstract Alkylation of aromatics with methanol is highly relevant for petrochemical production. Herein we have studied the co-reaction of methanol and benzene over H-ZSM-5 and H-beta using in-situ FT-IR at 350 C. Pronounced differences are seen for the catalysts. For H-ZSM-5, the Brnsted sites (3595 cm-1) are virtually unperturbed during steady state reaction. Upon feed admission (blue spectrum) methoxy groups on both Brnsted sites and silanol groups give rise to bands at 2980, 2970, and 2864 cm-1. As benzene diffuses into the catalyst pores, the methoxy groups are consumed and bands in the 3005-3130 cm-1 region, originating from aromatic CH stretching, and a weak feature at 2926 cm-1, corresponding to CH stretching in the methyl group of toluene (the methylation product), appear [1, 2]. For H-beta, however, the Brnsted sites (3601 cm-1) are always completely covered during reaction and the silanols (3736 cm1 ) are reduced to a large extent. Also, the methoxy bands are fully persistent. Clearly, for this reaction system, there are fundamental differences between the catalysts. It appears that all Brnsted sites are covered by methoxy groups during co-reaction over H-beta, in line with a two-step reaction mechanism via methoxy groups, whereas the Brnsted sites could be available for direct methylation without an intermediate in H-ZSM-5.
3737

3736

3005 - 3130

3005 - 3130

2970

2926

2957 2930
3000

3595

2864

3601

H-ZSM-5
3800 3700 3600 3500 3200 3100
-1

2980

H-Beta
2900 2800

3000

3800 3700 3600 3500 3200

3100
-1

2976

2900

2857
2800

Wavenumber (cm )

Wavenumber (cm )

Figure 1: FT-IR spectra of OH (3800-3500 cm-1) and CH (3200-2800 cm-1) stretching regions at increasing reaction times during co-reaction. Black line: evacuated zeolites; blue line: first spectrum after feed admission; green line: spectrum at steady state conditions. Left panels: H-ZSM-5. Right panels: H-beta. References [1] T. R. Forester, S.-T. Wong, and R. F. Howe, J. Chem. Soc., Chem. Commun. 1611 (1986). T. R. Forester and R. F. Howe, J. Am. Chem. Soc. 109, 5076 (1987). [2]

O46 Mercury Oxidation in Flue Gases

Karin Madsen1,2, Flemming Frandsen2, Anker Degn Jensen2 and Joakim Reimer Thgersen1 1 Haldor Topse A/S 2 Dept. of Chemical Engineering, DTU E-mail: kama@topsoe.dk Abstract Mercury emissions from coal-fired utility plants contribute significantly to the worlds total anthropogenic mercury emission. Mercury can be retained in air pollution control systems depending on the type of coal applied, the flue gas composition and operating conditions. The speciation of mercury in flue gasses is important to understand in order to optimize the mercury removal in the flue gas cleaning equipment. Oxidized mercury is soluble in water and is effectively removed in a wet scrubber or by adsorption on fly ash in fabric filters. The vanadium-based SCR (selective catalytic reduction) catalyst has been shown to have catalytic activity on elemental mercury oxidation in the presence of halogens, predominantly chlorine. In this presentation, the mechanism for catalytic oxidation of mercury across SCR is discussed. Mercury oxidation by chlorine over the SCR reactor is typically modelled as an Eley-Rideal mechanism, where either HCl adsorbs on the active site and reacts with gaseous Hg0 or visa versa. An inhibiting effect of NH3 on the mercury oxidation across SCR catalyst is seen across most experimental datasets. The effect is often explained by a competitive binding of NH3 and HCl/Hg0 to the same active site on the catalyst, presumably V2O5. Both Hg0, NH3 and HCl are experimentally seen to adsorb on the catalyst. The discussion will be based on: 1) transient data from lab-scale experiments studying sorption phenomena of Hg0, NH3 and HCl on SCR-catalyst and 2) steady-state data on the mercury oxidation from both lab- and full-scale experiments. The steady-state data are parametric studies across temperature, amount of catalyst and gas composition.

O47 Coupling of Methane with Li/MgO-Catalysts

Sebastian Arndt1, Guillaume Laugel1, Ulla Simon1, Stephan Heitz1, Torsten Otremba1, Yilmaz Aksu1, Almuth Berthold1, Matthias Driess1, Helmut Schubert1, Reinhard Schomcker1 1 Technische Universitt Berlin, Strae des 17.Juni 124, 10623 Berlin, Germany E-mail: schomaecker@tu-berlin.de Abstract The main component of natural gas is methane; its known resources are larger than those of crude oil. There is a big economical interest in the oxidative coupling of methane, which allows the coupling of methane to ethane or ethylene. CH4 + or 1 O2 C2H4 or C2H6 + H2O Making this reaction economically feasible, would allocate methane as carbon source for the chemical industry and solve most of the transport problems of natural gas. However, this reaction has not reached the commercial stage yet, due to a lack of suitable catalysts. One of the most investigated catalysts is Li/MgO, first described by Lunsford et al. [1]. Li/MgO is not only an active catalyst, but also suitable for quantum chemical calculations and surface science experiments, which enables further optimization of this catalyst. This is not the case for many other catalysts. Despite the intensive research, there are still many open questions, which need to be answered. Lunsford et al. proposed [Li+O-] centers as active center [1, 2], but experimental results of Mirodatos et al. did not fully agree with this [3]. This contradiction has not been solved yet. Some researchers report their catalyst to be stable, others describe sever deactivations. In some cases, the addition of CO2 was reported to avoid or even reverse the deactivation [4]. We prepared Li/MgO via different preparative routes (single source precursors, solid state chemistry, and wet impregnation techniques). A strong scattering of the catalytic results was observed. A correlation between catalytic performance and preparation and characterisation results, respectively, was not found. Mirodatos et al. observed a loss of Li in his deactivation experiments [3], we extended the duration of these experiments and found that after several days time on stream, the activity of Li/MgO approached the activity and selectivity of pure MgO. The results of our stability experiments indicate, that a high initial activity is a suicidal activities for Li/MgO, because at high conversions, the partial pressure of H2O is high, above a lethal partial pressure of H2O and the catalyst deactivates. Li/MgOs with a low initial activity did not show signs of severe deactivation. References [1] T. Ito and J.H. Lunsford, Nature 314, 721 (1985). T. Ito, J.X. Wang, C.H. Lin and J.H. Lunsford, J. Am. Chem. Soc. 107, 5062 (1985). [2] [3] C. Mirodatos, V. Perrichon, M.C. Durupty and P. Moral, Stud. Surf. Sci. Catal. 34, 183 (1987). [4] S.J. Korf, J.A. Roos, N.A. de Brujin, J.G. van Ommen and J.R.H. Ross, J. Chem. Soc., Chem. Commun. 1433 (1987)

O48 Snapshots of the catalyst structure during the partial oxidation of methane
Jan-Dierk Grunwaldt1, Bertram Kimmerle2, Alfons Baiker2, Pit Boye3, Christian G. Schroer3, Jan Sttzel4, Ronald Frahm4 1 DTU-Chemical Engineering, DK-2800 Kgs. Lyngby; present address: Institute for Chemical Technology and Polymer Chemistry (ITCP), KIT, D-76131 Karlsruhe 2 Institute for Chemical and Bioengineering, ETH Zurich, CH-8093 Zurich 3 Institut fr Strukturphysik, TU Dresden, D-01062 Dresden 4 Fachbereich C / Physik, Bergische Universitt Wuppertal, D-42097 Wuppertal E-mail: grunwaldt@kit.edu Abstract An attractive route for transforming methane or natural gas into liquid products is via their partial oxidation to hydrogen and carbon monoxide [1]. The reaction ignites at a characteristic temperature. Despite of the importance of this reaction still little is understood which is mainly due to the fact that the catalyst is highly dynamic and gradients in product composition and temperature distribution are found along the catalytic reactor. Therefore we studied the structure in more detail by in situ X-ray absorption spectroscopy (spatially and time-resolved) and temperature profiling. We report on changes in oxidation states during the ignition and extinction of the CPO of methane in a heated fixed-bed microreactor. Time resolved X-ray absorption spectra were taken in the subsecond time scale using the QEXAFS method [2] both at the Pt L3- and Rh K-edge (APS, Chicago and SLS, Switzerland), uncovering changes in the second or even subsecond time-scale during ignition and in the second time-scale during extinction [3]. In addition, X-ray transmission images were recorded in the millisecond range (ESRF, Grenoble). By appropriate data processing a reduction of the initially oxidized supported metals could be made visible by exploiting the change in X-ray absorption depicted in Fig. 1 as color change [4]. Strikingly, we observed that during heat-up when reaching the ignition temperature (switch from production of only CO2 and H2O to the formation of CO and H2; here at 330 C) single particles became first reduced at the end of the catalyst bed and a corresponding front formed, which propagated toward the reactor inlet. Snapshots of this ignition period at the outlet of the microreactor are depicted in Fig. 1. Simultaneously, temperature distribution and catalytic performance were monitored [4].

Figure 1. Reduction of single particles during ignition. (cf. reference [4]). References [1] A. T. Ashcroft, A. K. Cheetham, M. L. H. Green, P. D. F. Vernon, Nature 352 (1991) 225; J. R. Rostrup-Nielsen, Catal. Today 18 (1993) 305. [2] B.S. Clausen, H. Topse, R. Frahm, Advances in Catalysis 42 (1998) 315. [3] J.-D. Grunwaldt, M. Beier, et al., Phys. Chem. Chem. Phys. 11 (2009) 8779. [4] B. Kimmerle, J.-D. Grunwaldt, et al., J. Phys. Chem. C 113 (2009) 3037; selected as ESRF Highlight 2009.

P1 Co catalysed Fischer-Tropsch synthesis in biofuel production

Henrik Romar1,*, Riikka Lahti1,2, Pekka Tynjl1,2, Ulla Lassi1,2 Kokkola University Consortium Chydenius, Talonpojankatu 2 B, 67100 Kokkola, Finland 2 University of Oulu, Department of Chemistry, P.O.Box 3000, FIN-90014 University of Oulu Finland E-mail: henrik.romar@chydenius.fi
1

Abstract There is a great interest in finding new solutions for traffic fuels. One such solution is to convert biomass into synthesis gas by gasification and further convert it to biofuels, e.g. biodiesel. One process to convert gasified carbon-containing material to liquid hydrocarbons is the Fischer-Tropsch (FT) process which has mostly been used to produce liquid fuels from coal over supported Co or Fe catalysts. Until recently, there have been some few publications dealing with catalytic Fischer-Tropsch synthesis starting from biomass. [1-2] In this research several Co catalysts were prepared, developed and tested in the model reaction of H2 and CO. Two supports were tested; one pelleted, large pore -Al2O3 (support A) and one small particle Al2O3 with small pores (support B). Catalysts were prepared by incipient wetness impregnation using Co(acetate)2 or Co(NO3)2 as precursor salts which were impregnated onto the supports (-Al2O3) followed by drying, calcination and reduction. In addition to Co, small portions of Ru from Ru(NO)(NO3) were added to some catalysts in order to promote the reduction. The final Co content of the catalysts, verified by ICP, was ranging from 10 to 20 mass-%. Each catalyst was first tested by feeding H2 and CO at molar ratios ranging from 1:1 to 2:1 into a fixedbed catalytic reactor using pressures from 5 to 9 bars and kept at temperatures ranging from 220 to 340 C. Reaction products were collected in two separate traps, one heated and one cooled. Liquid hydrocarbons formed were analysed by FT-IR and GC-FID/GC-MSD. The best catalyst compositions were used in experiments with a synthetic gas containing H2 20 vol-%, CO 20 vol-%, CO2 10 vol-%, CH4 1,5 vol-%, and N2 47,5 vol-%. This gas composition is very close to the real product gas from biomass gasification (after tar removal), although the product gas composition to some extent varies depending on the biomass quality, gasifier type and gasification temperature. Based on the preliminary results, two different CoRu catalysts showed rather high activities in FT synthesis to biodiesel (C6-C25). These catalysts were based on either Co(acetate)2 on the support A or Co(NO3)2 on the support B. On the other hand Co(acetate)2 on the support B had no or very low activity in FT synthesis. References [1] Lgdberg et al., Applied Catalysis B: Environmental 89 167 (2009). [2] Tristantini et al., Fuel Processing Technology 88 643 (2007)

P2 ZnO supported on Al2O3, SiO2, TiO2 and ZrO2 for the Activation of Methane, Ethane and Propane
Sebastian Arndt1, Burcu Uysal2, Torsten Otremba1, Yilmaz Aksu1, Reinhard Schomcker1, 1 Technische Universitt Berlin, Strae des 17.Juni 124, 10623 Berlin, Germany 2 Akdeniz University, Fen-Edebiyat Fakltesi, Kimya Blm, Antalya, Turkey E-mail: schomaecker@tu-berlin.de Abstract The known resources of natural gas are large, therefore there exists a big economical interest in converting the main components (CH4 as major component, C2H6 and C3H8 as minor components) into value added products, e.g. olefins [1]. Direct routes to convert these compounds into the desired olefins are the oxidative coupling of methane and the oxidative dehydrogenation of ethane and propane [1, 2, 3]. 1. oxidative coupling of methane (OCM) CH4 + or 1 O2 C2H4 or C2H6 + H2O 2. oxidative dehydrogenation of ethane (ODE) C2H6 + O2 C2H4 + H2O 3. oxidative dehydrogenation of propane (ODP) C3H8 + O2 C3H6 + H2O However, these processes have still not reached commercial application, due to the lack of suitable catalysts. ZnO is considered to be a suitable catalyst. But it has been shown, that it suffers from severe sintering and deactivation, which starts already below reaction temperature [4]. One possibility to improve the thermal stability and avoid deactivation is the usage of a support. Most supports influence the catalytic performance of the supported material, which also has to be considered. We prepared different loadings of ZnO supported on Al2O3, SiO2, TiO2 and ZrO2. The catalytic performance for the C-H activation for lower alkanes was investigated for each catalyst. A comparison of the results allowed an evaluation of the effect of the different support materials on the activity. The experiments show, that for different reactions the support can increase or even decrease the activity, and that the results strongly depend on the kind of support used and not on the loading of ZnO. References [1] [2] [3] [4] J.H. Lunsford, Catal. Today 63, 165 (2000). E. Kondratenko and M. Baerns in ''Handbook of Heterogeneous Catalysis'', Wiley-VCH, Chapter 13.17, 3010 (2008). S.F. Hkonsen and A. Holmen in ''Handbook of Heterogeneous Catalysis'', Wiley-VCH, Chapter 14.11.2, 3384 (2008). S. Arndt, Y. Aksu, M. Driess and R. Schomcker, Catal. Lett 131, 258 (2009)

P3 The role of monomeric iron during the selective catalytic reduction of NOx by NH3 over Fe-BEA zeolite catalysts
Martin Hj1,2, Matthias Josef Beier2, Jan-Dierk Grunwaldt2, Sren Dahl1,3 1 Haldor Topse A/S, Nymllevej 55, DK-2800 Kgs. Lyngby, Denmark. 2 DTU Chemical Engineering, Technical University of Denmark, 2800 Lyngby, Denmark. 3 DTU Physics, Technical University of Denmark, 2800 Lyngby, Denmark. E-mail: mh@kt.dtu.dk Abstract A series of highly active Fe-BEA iron zeolite catalysts for selective catalytic reduction (SCR) of NOx with ammonia have been prepared by incipient wetness impregnation and aqueous ion exchange with Fe(NO3)3 solutions [1]. While the catalysts were stable during short term hydrothermal ageing, extended periods of ageing did reduce activity. The catalysts were investigated by diffuse reflectance UVvis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, ammonia temperature programmed desorption (NH3-TPD), X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) both ex-situ and in-situ with online gas analysis to measure catalytic activity. UVvis, EPR and EXAFS showed that low iron loadings ( 1.2 wt.% Fe) resulted in mostly iron monomers, especially for the ion exchanged samples. In contrast a mixture of monomers, oligomers and hematite particles was formed at intermediate to high loadings (2.55.1 wt.% Fe). Linear combination analysis of UVvis spectra, with real spectra and one Gaussian as basis, was used for quantifying the three iron species. A good correlation between iron monomer content and NO conversion was observed. In-situ XANES and EXAFS showed that heating in oxygen atmosphere removes water from the iron coordination sphere and the resultant vacant positions are occupied by NO, NH3 or H2O upon exposing the catalyst to a gas mixture of NO, NH3 and O2 in He. Heating in this gas mixture gave a distinct correlation between the catalytic performance and the oxidation state of iron, which is more pronounced in the catalysts where mostly iron monomers are present. Iron was more partially reduced when the SCR activity increased as depicted in Figure 1. These results support a mechanism where the oxidation of iron or NO is the rate determining step.
100 90 80 70 60 50 40 30 20 10 0
1,0

x(NO) x(NH3)

Frac. of ox. species

0,8 0,6 0,4 0,2 0,0 Frac. of ox. species

x/%

180 200 220 240 260 280 300 320

Figure 1: Oxidation state of iron (right) and conversion of NO and NH3 (left) during in-situ XANES spectroscopy. [1] M. Hj, M. J. Beier, J.-D. Grunwaldt and S. Dahl, Appl. Catal. B 93, 166 (2009).

T / C

P4
THE PRODUCTION of MOTOR FUEL and CHEMICAL COMPOUNDS from the PRODUCTS of THERMAL PROCESSING of OIL SHALES Yu.A.Srtizhakova, A.L.Lapidus Samarsky State Technical University, Samara, ul. Molodogvardeiskay, 144, e-mail: nich@samgtu.ru N.D.Zelinsky Institute of Ogranic Chemistry RAS, Moscow, Leninsky Pr., 47, tel (fax): (499)1355303, e-mail: albert@server.ioc.ac.ru Qualified using of some solid combustible minerals with low metamorphism extent: oil shales, peat and wood for production of fuel and chemical products is a very actual problem for our country because of their large resource. It is possible to carry out two principal different ways of their use: thermal processing and gasification with following processing of gas products. Production of synthesis gas with composition CO:H2=1:2 (vol.) is possible at gasification of oil shales. This gas is converted into the mixture of hydrocarbons over cobalt catalysts at 170-280oC at 1-30 atm. The hydrocarbons can be used as motor, including diesel, or reactive fuel. We proposed the effective catalysts at which conversion of synthesis gas in liquid products equals 80-90%. The questions connected with production mixed diesel fuels containing 5-15% of C5-C10 nparaffins and obtaining from synthesis gas over Co-systems will be elucidated in the report. These fuels are characterized by high ecologies because of low CO, CO2 and CnHm contents in exhaust gases. The results of there fuels tests in engine of interior combustion are given in the report.

P5 Gasification of oil-shales for hydrogen containing gas production

1

A. Lapidus1, F. Zhagfarov, A. Kozlov, T. Avakyan, Y. Strizhakova2 Gubkin Russian State University of Oil and Gas, Moscow, Leninskii Prosp. 65 2 Samara State Technical University, Samara, Molodogvardeiskaya St. 144 E-mail: albert@ioc.ac.ru

Currently, oil and gas are far and wide used as the main sources of raw materials for power and chemical industry. However, reduction of explored reserves and operating problems in production activity lead to increase in oil and gas prices. Therefore economically developed countries give special consideration to the matter of solid fossil fuels application. In this case worldwide spread oil-shales can be regarded as important potential feedstock for fuel, power and chemical production. Oil-shales are considered to be perspective feedstock for synfuels production and chemical industry. Considerable content of hydrogen in organic matter and higher yield of crude shale oil under thermal decomposition distinguish oil-shales from other solid fuels. In this work, the research results of thermolysis of oil-shales from Kashpir (Russia) and Baltic (Russia, Estonia) shalefields are presented. In order to enhance the process efficiency catalytic conversion stage, NiO was used as catalyst, was carried out. Obtained results shows that for Kashpir oilshales content of hydrogen in gaseous products is higher than for Baltic oil-shales (Table 1). The last one are characterized by large share of 2 in gaseous products (64-62 %), indicating considerable amount of mineral components. Obtained data shows that quite intensive conversion of oil-shales takes place under sufficiently high temperatures (500-650). Also it should be noted that for Kashpir oilshale concentration of hydrogen in gasification products reaches 89,8%. Table 1 Kashpir and Baltic oil-shales thermolysis gas composition (%) Reaction temp. () 500 500 (NiO) 600 600 (NiO) 650 650 (NiO) 2 25,6 40,9 55,3 80,1 73,1 89,8 Kashpir oil-shales 2 15,9 12,1 8,5 14,8 7,2 5,1 2,1 2,5 4,6 6,2 3,8 2,4 4 33,9 28,5 17,8 12,1 8,0 3,9 2 8,7 19,6 31,1 35,4 32,8 49,9 Baltic oil-shales 2 16,2 62,5 16,6 42,7 8,0 46,7 4,7 53,2 7,9 49,3 6,7 36,0 4 14,4 21,1 11,2 6,7 10,0 7,4

P6 Molten salts stabilised palladium nanoparticles phosphine-free catalyst for the carbonylation of olefins, alcohols and benzyl halides
1

A. L. Lapidus1, O.L. Eliseev1, T.N. Bondarenko1, N.H. Chau2 N.D. Zelinsky Institute of organic Chemistry RAS, 47 Leninsky prosp., Moscow, Russia 2 Gubkin Russian State University of Oil and Gas, 65 Leninsky prosp., Moscow, Russia E-mail: oleg@server.ioc.ac.ru

Abstract Palladium catalysed hydroxycarbonylation of olefins, alcohols and halides is convenient rout to correspondent carboxylic acids and their esters. Important advantage of catalytic carbonylation reactions is high value of atom efficiency, up to 100%. However, catalyst recovering still challenging problem in hydroxycarbonylation as well as in other homogeneous transition metal catalysed reactions. Another drawback of such processes is necessity in expensive and readily degradable phosphine ligands. We propose simple and efficient catalytic system based on ligand-free palladium dissolved in NBu4Br melt (liquid at the reaction conditions). Ethylene, long-chain -olefins, styrene, benzyl alcohol, 1phenylethanol and some other alcohols were successively converted into correspondent carboxylic acids and their esters. Also, hydroxycarbonylation of benzylic halides leads to arylacetic acids with high yields. Importantly, stoichiometric amount of base is not needed to complete the reaction, unlike traditional protocol for halides carbonylation. Catalytic system can be used repeatedly by simple extraction of products with hexane, and reloading operation can be performed on air without loss of catalyst activity at that. Effect of molten salt nature and other factors on catalyst activity and regioselectivity is analyzed. Palladium colloids were supposed to form and serve as reservoir for active species in ligand-free catalytic system.

Figure 1: TEM image of Pd nanoparticles in dodecene-1 carbonylation reaction mixture

P7 Chemoenzymatic combination of oxidase enzymes with titanium silicalite-1

Peter N. R. Vennestrm1,2, Sven Pedersen3, Claus H. Christensen1, Jan-Dierk Grunwaldt2,4, John M. Woodley2 1 Haldor Topse A/S, Nymllevej 55, DK-2800 Lyngby, Denmark, 2 Department of Chemical and Biochemical Engineering, Technical University of Denmark, DK-2800 Lyngby, Denmark, 3 Novozymes A/S, Krogshjvej 36, DK-2880 Bagsvrd, Denmark, 4 Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, D-76131 Karlsruhe, Germany E-mail: pnrv@topsoe.dk Abstract In a future chemical industry based on renewable resources the integration of heterogeneous chemical catalysis with biocatalysis, especially using enzymes, will become increasingly important [1]. In some cases the combination may be tailored so that both catalysts may work together and the advantages of one-pot combinations fully exploited. Herein we report the combination of a truly integrated heterogeneous chemoenzymatic combination of oxidase enzymes with the hydrogen peroxide active chemical catalyst titanium silicalite-1 (TS-1). In this combination an enzymatic substrate is oxidised using air as a safe oxidant, and the hydrogen peroxide generated is used in a chemical reaction where the reactant is oxidised simultaneously. In this way the hydrogen peroxide by-product should not be decomposed and wasted [1], but can be exploited in the chemical reaction, following the directions of green chemistry. An exemplified reaction scheme with the oxidation of glucose into gluconic acid using glucose oxidase (E.C. 1.1.3.4, GOx) and resultant oxidation of allyl alcohol to glycidol is given in Scheme 1.
OH HO HO O OH OH GOx O2 O O HO OH OH OH O TS-1 H2O HO OH OH OH OH OH O OH

OH + H2O2 (by-product)

Scheme 1. Principle scheme for the chemoenzymatic combination of glucose oxidase oxidizing -D-glucopyranose to Dglucono-1,5-lactone, which hydrolyzes in water to D-gluconic acid. Hydrogen peroxide is generated as a by-product and used in the oxidation of allyl alcohol to glycidol with a TS-1 catalyst

For the reaction shown in Scheme 1 and similar reactions with pyranose-2-oxidase (E.C. 1.1.3.10, P2O) and various chemical substrates, the oxidase enzyme was linked to the TS-1 surface using 3aminopropyltriethoxysilane and glutaraldehyde to produce an integrated catalyst system. The one-pot heterogeneous combinations were tested with GOx [2], P2O and several chemical reactants ranging from alcohols to alkenes giving positive results. This demonstrates new opportunities in chemoenzymatic combinations. Further investigation will however be required to uncover the full potential, and to evaluate if it will be applicable to fine chemical production or in the production of commodity chemicals as well. In particular, issues like separation of products from the reaction mixture, which require new innovative solutionse and catalyst deactivation have to be addressed. Nevertheless, it offers a new approach to a chemical industry in search of new catalyst systems able to operate under ambient conditions and most likely using aqueous solvents. [1] P. N. R. Vennestrm, C. H. Christensen, S. Pedersen, J.-D. Grunwaldt, J. M. Woodley, ChemCatChem 2, 249 (2010) [2] P. N. R. Vennestrm, E. Taarning, C. H. Christensen, S. Pedersen, J.-D. Grunwaldt, J. M. Woodley, ChemCatChem (submitted for publication 2010)

P8 Nitrogen tolerant hydrodesulfurization catalysts based on Rh and Ru promoted Mo/Al2O3

Z. Vt, L. Kalua and D. Gulkov ICPF of the ASCR, v.v.i., Rozvojov 135, 165 02 Prague, Czech Republic E-mail: vit@icpf.cas.cz Hydrodesulfurization (HDS) is generally deeply inhibited by nitrogen compounds when carried out over conventional CoMo/Al2O3 catalysts. Recently, Mo/Al2O3 sulfided catalysts promoted by noble metals (Rh, Ru) showed higher HDS activities than CoMo in simultaneous HDS/HDN of thiophene (TH) and pyridine (PY)[1]. The goal of this work was to compare the inhibitive effects of different amounts of PY on HDS of TH over both types of catalysts and try to explain the lower sensitivity of noble metal promoted catalysts to this inhibition. The promoted catalysts contained 0.3-0.6 wt.% of Rh (Ru) and 9 wt.% Mo on Al2O3. They were prepared by impregnation of oxidic and sulfided Mo/Al2O3 by acetylacetonates of Rh and Ru and accordingly denoted by letters (o) and (s). Two CoMo/Al2O3, one prepared and one industrial (S344), were studied for comparison. All catalysts were sulfided by 10 % H2S in H2 at 400oC/1h. The composition of catalysts was determined by ICP/AAS. The HDS was carried out at 320oC/2 MPa in a flow integral reactor. The feed contained 240 ppm TH and different amounts of PY (0 - 220 ppm) in H2. The HDS activity was expressed by pseudo-first-order rate constants kTH per kg of catalyst. The nitrogen tolerance of the catalysts was defined by the ratio kTH220 to kTH0, evaluated with added 220 ppm PY and without PY, respectively. It was found, that both CoMo catalysts were most active in the absence of PY. However, already 12 ppm PY severely suppressed their activities. Rh (Ru) promoted Mo samples were inhibited much less and become more active in the presence of PY than CoMo/Al2O3. Their higher nitrogen tolerance was ascribed partly to their higher C-N bond hydrogenolysis activities, facilitating the removal of nitrogen inhibitors by HDN and releasing in this way part of sites for HDS. The second reason was most likely the higher own tolerances of the free Rh (Ru) sulfides in the bimetallic systems. Greater effects were achieved when Rh and Ru were deposited on the sulfided Mo/Al2O3 (s catalysts). Table 1. Nitrogen tolerance of catalysts. ___________________________________________________________________________ Catalyst Mo CoMo RuMo(o) RhMo(o) RuMo(s) RhMo(s) ___________________________________________________________________________ 0.08 0.12-0.18 0.21 0.28 0.38 0.54 kTH220/kTH0 ___________________________________________________________________________ Acknowledgement The support of the Czech Science Foundation (grant 104/09/0751) is acknowledged. References [1] Z. Vt, J. Cinibulk and D. Gulkov, Appl. Catal. A 272, 99 (2004).

P9 Catalytic Performance of Mixed-addenda Heteropolyanions as Inorganic Solid Catalysts in Lactonization of Various Diols
Ali Gharib1,2,* , F.F. Bamoharram1, Manochehr Jahangir1, Mina Roshani1 1 Department of Chemistry, Islamic Azad University, Mashhad, IRAN 2 Agricultural researches and services Center, Mashhad, IRAN * E-mail: aligharib5@yahoo.com Lactones have deserved great interest in synthetic and natural products chemistry. These structures occur extensively in the natural world and their biological and pharmacological activities have been widely studied.[1-3] They can be also used for the synthesis of polyesters. [4] Several catalytic synthetic methods for lactones have been developed and reported during these recent years. [1,5,6] In two last decades research on heteropolyacids, which are a type of inorganic solid catalysts has attracted much attention. A heteropolyacids is an oxide cluster, which has a type of phosphorus/silicon oxo acid and oxo acids with molybdenum, tungsten and other elements. In this research potasium salts of the monosubstituted Keggin polyoxometalates, [PW11MO40]7- , (M= Co(II) , Ni (II), Cu(II) , Zn(II), were used as catalysts for lactonization of 1, 4-butane diol, 1, 6 hexane diol and 1, 2-benzene dimethanol, in the presence of hydrogen peroxide as an oxidant . The effects of various parameters such as amount of the oxidant and diol, solvent type, temperature and reaction time have been studied.

Lacunary structures XM9O34nAcknowledgements: Author is thankful from Dr. Mina Roshani and F.F. Bamoharram and Islamic Azad University, Mashhad. References: [1] A. K. Picman, Biochem. Syst. Ecol., 1986, 14, 255. [2] K. L Dueholm, L. B. Pederson, Synthesis., 1992, 1. [3] D. W. Robertson, J. H. Krushinski, B. G. Utterback, R. F. Kauffman, J. Med. Chem., 1989, 32, 1476. [4] L. F. Bjeldanes, J. Org. Chem., 1977, 42, 2333. [5] M. A. Weidner Wells, A. Decamp, P. H. Mazzocchi, J. Org. Chem., 1989, 54, 5746. [6] T. F. Al Alzemi, L. Kondaveti, K. S. Bisht, Macromolecules., 2002, 35, 3380.

P10 Catalytic Performance of Preyssler Heteropolyanions as HomogeneousCatalysts in Phenacetin(anti-inflammatory) of p-Aminophenol

1

Ali Gharib1,2,* , Manochehr Jahangir1, Mina Roshani1 Department of Chemistry, Islamic Azad University, Mashhad, IRAN 2 Agricultural researches and services Center, Mashhad, IRAN * E-mail: aligharib5@yahoo.com

Heteropolyacid (HPA) compounds are the objective of research for a long time.The reactions catalyzed By them both in heterogeneous and homogeneous systems have been reviewed by many researchers [1].Catalysis of keggin heteropolyacid has at tracted much interest since seventies.The heteropolyacid possesses the dual catalytic functions of strong acidity and oxidizing ability.HPA will be expected as an alternative acid catalyst to improve several organic processes which employ conventional acids [2].In aqueous solution HPA such as PW, SiW, Preyssler"s anion and PMo are strong fully dissociated acids. HPAs in solution are stronger them the usual mineral acids such as HCl, Sulfuric acid, and etc [3]. teropoly acids (HPAs) are well defined molecular clusters that are remarkable for their molecular and electronic structural diversity and their significance is quite diverse in many areas, e.g., catalysis, medicine, and materials science [2]. HPAs are complex proton acid that incorporate polyoxometalate anions (heteropolyanions) having metal-oxygen octahedra as the basic structural units and catalysis by them is a field of increasing importance [3]. [NaP5W30O110]14-, the socalled Preysslers anion, Na+ is encrypted inside a central cavity formed by five PW6O22 units arranged in a crown [4], as shown schematically in Fig. 1. Acylated aromatic amines are important in over-the-counter headache remedies. Of course, phenacetin, salicylamide, salicylacetamide and ethenzamide are using directly for antiflammatory and anti-pyretics, also, they are compounded with drugs of anti- flammatory and antipyretics in pharmaceutical industries. Phenacetin is an important analgesic being used to relieve headache, neurotic pains and rheumatism. We used from heteropolyacids as catalyst in the synthesis of Acetaminophen,Phenacetin and obtained high yields under mild and green conditions.The recovered solids were recycled and reused as catalyst for new reactions withot loss of catalytc activities, these catalyst are inexpensive, clean,noncorrosive in industrial, green, eco-friendly, environmentally friendly.
O NH2 HN CH3 HPA, Toluene reflux OH Acetaminophen OCH2CH3 Phenacetin HN O CH3

O O

HPA, r.t OH p-Aminophenol

Figure 1. Structure of [NaP5W30O110]14- polyhedral form showing WO6 octahedra and the central Na (open circle).

References: [1]T. Okuhara, N. Mizuno, M. Misono, Adv. Catal. 41, 113 (1996). [2]M. A. Schwegler, J. A. Peters, H. Van Bekkum, J. Mol. Catal. 63, 343 (1990). [3] S. Shikata, M. Misono, Chem. Commun. 12, 1293 (1998). [4] F. F. Bamoharram, M. M. Heravi, M. Roshani, M. A. Gharib, M. Jahangir, J. Mol. Catal. A: Chem. 2006, 252, 90.

P11 Catalytic Synthesis of 2,5-Disubstituted Oxazoles Using Preyssler Homogeneous Heteropolyacid Catalysts
Ali Gharib1,2*, Manouchehr Jahangir1, Mina Roshani1
1

Department of Chemistry, Islamic Azad University, Mashhad, IRAN 2 Agricultural Researches and Services Center, Mashhad, IRAN E-mail: aligharib5@yahoo.com

Catalysis by heteropoly acids (HPAs) and related polyoxometalate compounds is a field of increasing importance, attracting increasing attention worldwide, in which many new and exciting developments are taking place in both research and technology [1]. Tungstophosphoric (H3PW12O40.xH2O) acid (TPA) type of heteropoly acid was used as active solid acid catalysts and impregnated on the activated carbon (AC). The structure of Keggin compounds, shown in Figure.1, comprises four trigonal groups of edgesharing MO6 octahedra, each group sharing corners with neighboring groups and with the central tetrahedron (-structure). In each octahedron the metal is displaced towards the terminal oxygen atoms. This structural arrangement leads to the formation of a spherical polyanion.

Figure 1. Heteropolyanion with the Keggin structure Synthesis of 2,5-Disubstituted oxazoles were carried out by treatment of aromatic -methyl ketones and nitriles using Keggin heteropolyacid catalyst, [H3PW12O40] in mild conditions. Introducing clean processes and utilizing eco-friendly and green catalysts which can be simply recycled at the end of reactions have been under permanent attention and demands. We describe a convenient and efficient protocol for the synthesis of the synthesis of 2,5-Disubstituted Oxazoles via aromatic -methyl ketones, with nitriles using [H3PW12O40] as a green recyclable and heterogeneous catalyst. The green catalysts can be easily recovered and recycled with retention of their initial structure and activity. In the presence of heteropolyacids, the aromatic -methyl ketones can react readily with nitriles to produce oxazoles in good yields. After the reaction, heteropolyacids catalysts can be recovered and reused without loss of catalytic activity. We used from a heteropolyacid catalyst after recovery and recyclable in synthesis of 2Methyl-5-phenyl oxazole and obtained a similar yield .
O N + Ar CH 3 RC N Heteropolyacid reflux Ar O R

References: [1] I. V. Kozhevnikov, Heteropoly Acids and Related Compounds as Catalysts for Fine Chemical Synthesis, Catal., Rev. Sci. Eng. 37(2), 311 (1995).

P12 Thermal ageing behavior of Pt-only TWC converters under simulated exhaust conditions: Effect of rare earths (CeO2, La2O3) and alkali (Na) modifiers
V. Matsouka, M. Konsolakis*, I.V. Yentekakis* Laboratory of Physical Chemistry and Chemical Processes, Department of Sciences, Technical University of Crete, 73100 Chania, Crete, Greece. *E-mails: mkonsol@science.tuc.gr (M. Konsolakis); yyentek@science.tuc.gr (I.V. Yentekakis) Abstract Air pollutants (NOx, CO, HCs) emitted from mobile sources significantly contribute to a variety of environmental problems, such as greenhouse effect and ozone depletion. Nowadays, Three-Way Catalytic converters (TWCs) employ a well established technology for automotive emission control, based mainly on Pt, Pd and Rh metals. However after ~35 years of their use there are several operational and economic aspects which have to be considered, such as i) the reduction or elimination of rare and expensive Rh (the key component for the NOx abatement), ii) the control of toxic pollutants during cold start period due to tightened emissions legislation; to this direction, mounting TWCs with enhanced thermal stability close to the exhaust part of engine, where the catalyst can be exposed to temperatures up to 1000oC, is being explored. Thus, the effect of both structural stabilizers and surface promoters on the activity and thermal stability of TWCs constitutes a subject of considerable interest in the area of environmental catalysis [1]. Our recent promising achievements obtained with structural (CeO2/La2O3) and surface (Na) modified monometallic Pt/Al2O3 TWCs [2], prompted us to expand our studies, investigating here the effect of thermal ageing (calcination in air at 900oC for 5h) on the surface and catalytic properties of Pt-only TWCs under simulated exhaust conditions. For the sake of comparison the catalytic and thermal behavior of commercial bimetallic Pt/Rh TWCs were tested under similar conditions. The evolution of surface behavior was identified by means of diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) over both fresh and aged catalysts under exactly the same conditions imposed on activity tests. The results reveal enhanced catalytic performance of Na-promoted TWCs in either fresh or aged state; their conversion and selectivity performance is similar to that of commercial TWCs which however contain 4.5-fold higher noble metal loading, revealing the practical and economical advantages of Na-promoted TWCs. References [1] Neil R. Collins and Martyn V. Twigg, Topics in Catalysis, 42-43 (2007) 323. [2] I.V. Yentekakis, M. Konsolakis, I.A. Rapakousios, V. Matsouka, Topics in Catalysis 42-43 (2007) 393.

P13 Operando XANES for structure activity studies: Combustion of methane on Pd/Al2O3 under genuine conditions
M. Santhosh Kumar, M. H. Aguirre, A. Weidenkaff, D. Ferri Empa, Lab. for Solid State Chemistry and Catalysis, berlandstrasse 129, CH-8600 Dbendorf, Switzerland; e-mail: santhosh.matam@empa.ch Palladium based catalysts are efficient for methane combustion in a wide temperature range. The catalysts often exhibit improved combustion activity in the low temperature region than it did before being exposed to high temperatures and thereby exhibit the so called hysteresis in the reaction rate. However, the intriguing behaviour of Pd in the catalysts is not yet completely understood and is still a subject of debate [1,2]. As such, in situ spectroscopic studies on the behaviour of Pd during the reaction are scarce and moreover they are limited to low temperatures where the behaviour of Pd cannot be understood. Therefore, the objective of this work is to monitor commercially relevant 2 wt.% Pd/Al2O3 catalyst by X-ray absorption spectroscopy (XAS) during combustion of methane in a lab scale fixed bed reactor coupled with a mass spectrometer to obtain better knowledge on the catalytic behaviour of Pd. Complete methane conversion while heating is observed at around 650K and it remains 100% even up to 1123K (Fig. 1). The corresponding operando XANES spectra indicate that Pd is in an oxidized state up to 1000K and above this temperature Pd oxide is largely reduced.

Fig. 1. Methane conversion profiles on Pd/Al2O3 during heating and cooling and the corresponding operando XANES spectra. STEM images of the catalyst before and after the reaction cycle are shown in the insets. During cooling, conversion remains 100% up to 950K. Then the significant loss in the combustion activity is observed between 950 and 680K with a maximum loss of around 40% at 862K. The corresponding XANES spectra reveal that Pd is in a reduced state between 950 and 690K. Below 690K, Pd completely reoxidizes and the catalyst again exhibits 100% conversion. These results evidence that Pd oxide species are the active sites for the combustion of methane, in particular below 950K and, above this temperature reduced Pd can also catalyze the reaction. EXAFS, STEM and CO chemisorption studies on the fresh and used catalysts indicate that Pd oxide nanoparticles undergo restructuring and coalesce during the reaction cycle. This in turn led to improved combustion activity at low temperatures while cooling, suggesting the reaction is structure sensitive. References [1] R.J. Farrauto, M.C. Hobson, T. Kennelly, E.M. Waterman, Appl. Catal. A 81, 227 (1992). [2] M. Santhosh, A. Eyssler, P. Hug, N. Vegten, A. Baiker, A. Weidenkaff, D. Ferri, Appl. Catal. B 94, 77 (2010).

P14 Dry reforming of methane with carbon dioxide over Ni/MgO-ZrO2 catalysts
D.A. Bulushev1, B.M. Nagaraja1, S. Beloshapkin2, J.R.H. Ross1 1 CPI, CES, University of Limerick, Limerick, Ireland, 2 Materials & Surface Science Institute, University of Limerick, Limerick, Ireland E-mail: dmitri.bulushev@ul.ie Abstract Carbon dioxide could be catalytically converted to synthesis gas in the reaction with methane (dry reforming) at high temperatures. Often Ni catalysts are used as they are cheaper than those based on noble metals. However, one of the main problems of these catalysts is deactivation provided mainly by carbon deposition. Ni/MgO catalysts have been reported as being quite active and stable. Addition of ZrO2 to the MgO support may lead to more active and mechanically stable catalysts as compared to those using unpromoted MgO. The present research was aimed to the development of active and stable Ni/MgO-ZrO2 catalysts. The importance of the MgO/ZrO2 ratio, the catalyst preparation method, the pre-treatment and the Ni loading have all been shown. Impregnation of the calcined support with Ni nitrate followed by reduction in hydrogen at 1023 K gave much more active and stable catalysts as compared to the catalysts prepared by co-precipitation or catalysts prepared by impregnation followed by calcination at 1073 K. Calcination may provide Ni2+ cations migration into the bulk forming a solid solution and decrease of the active surface Ni sites concentration. A 10 wt.% Ni/MgO-ZrO2 catalyst had a high activity and stability within 15 h (Fig. 1) similar to that of a 10 wt.% Ni/MgO catalyst and a much higher activity than that of a 10 wt.% Ni/ZrO2 catalyst. Almost no carbon deposition was found for the Ni/MgO-ZrO2 catalysts in a CH4/CO2 (1:1) mixture at 1023 K. However, deactivation probably provided by Ni2+ cations migration into the bulk and sintering was observed for the samples with low Ni content (1 and 5 wt.%) (Fig. 1). An explanation of the observed behaviour of the Ni/MgO-ZrO2 catalysts was proposed based on the presence of highly dispersed Ni particles (5-10 nm) over MgO and NiO/MgO solid solution stabilized by zirconia. The catalysts were characterised by XRD, XPS, HRTEM/EDS and BET surface area measurements.

Figure 1. Dry reforming of methane over Ni/MgO-ZrO2 catalysts with different Ni content at 1023 K

P15 Characterization and catalytic activity of new metal-organic frameworks resulted from self-assembly of Ph3SnCl, K[Cu(CN)2] and nitrogen donor ligands
Safaa El-din H. Etaiw, Abeer S. Elsherbiny and Ahmed S. Badr El-din Chemistry Department, Faculty of Science, Tanta University, 31527-Tanta, Egypt E-mail: safaaetaiw@hotmail.com Abstract Metal-organic frameworks (MOFs) provide porous materials with a wide range of applications which includes separation, sensing, catalysis, conductivity and gas storage [1-3]. New five metal-organic frameworks (MOFs) of the general composition [Ph3SnCu(CN)2.L] where L = pyrazine (pyz) 1, methylpyrazine (mepyz) 2, 4,4'-bipyridine (bpy) 3, trans-1,2-bis(4-pyridyl)ethene (tbpe) 4 or 1,2-bis(4pyridyl)ethane (bpe) 5 have been synthesized and characterized to test their potential applications as catalysts. The products were characterized by elemental analysis, X-ray powder diffraction, thermogravimetric analysis and IR, mass, NMR, UV-visible, and emission spectra. These compounds are strong fluorescent in the solid state. The catalytic studies on MOFs 1-5 indicate that they are active catalysts for the degradation of Metanil yellow which is azo-dye by dilute solution of hydrogen peroxide as oxidant. The reaction is pseudo-first order kinetic with respect to Metanil Yellow. The rate constant of the degradation reaction of Metanil Yellow decreases in the following order 4>3>5>2>1. Detailed kinetic measurements were carried out for the degradation of Metanil yellow using MOF 4, as a catalyst. The activation parameters of the reaction have been estimated and a possible mechanism has been proposed. References [1] L. L. Johnston, J. H. Nettleman, M. A. Braverman, L. K. Sposato, R. M. Supkowski and R. L. LaDuca, Polyhedron , 29, 303 (2010). [2] D. Sun, G.-G. Luo, N. Zhang, Q.-J. Xu, Y.-C. Jin, Z.-H. Wei, C.-F. Yang, L.-R. Lin, R.-B. Huang and L.-S. Zheng, Inorg. Chem. Commun. 13, 306 (2010). [3] J. T. Culp, S. Natesakhawat, M. R. Smith, E. Bittner, C. Matranga and B. Bockrath, J. Phys. Chem. C 112, 7079 (2008).

P16 Effect of cobalt particle size on Fischer-Tropsch hydrocarbon selectivities for -alumina as support
1

Shreyas Rane1, yvind Borg2, Erling Rytter1,2, Anders Holmen1 Department of Chemical Engineering, NTNU, NO-7491, Trondheim, Norway 2 Statoil R&D Research centre, Postuttak, NO-7005, Trondheim, Norway E-mail: shreyas.rane@chemeng.ntnu.no

Abstract Fischer-Tropsch synthesis is a key reaction in the production of long chain hydrocarbons from natural gas, biomass, and coal. Supported cobalt catalyst is the preferred catalyst in the conversion of natural gas derived synthesis gas. Significant variations in the selectivity of higher hydrocarbons have been observed on different supports (-Al2O3, SiO2, TiO2) [1]. It has also been shown that -Al2O3 always give higher C5+ selectivity than -Al2O3 [2]. In order to study the effect of support properties on the C5+ selectivity, -Al2O3 was prepared from -Al2O3 by heat treatment. The catalysts were then prepared by one-step incipient wetness impregnation where the proportion of deionised water and ethylene glycol in the impregnation solution was varied to produce Co3O4 crystallites with different sizes. Cobalt particle sizes of 2 to 12 nm (H2 chemisorption, O2 titration) were obtained. The Fischer-Tropsch synthesis was carried out at 20 bar, 483 K and H2/CO=2.1 for 100 h time on stream in a fixed bed reactor.
85 C5+ selectivity (%) 9 7 C4=/C4C3=/C35 3 1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Cobalt particle size, nm
C5+ selectivity (%) 90 2,6 C3=/C3-, C4=/C4- ratio 2,4 C4=/C4C3=/C32,2 2

83 81 79 77 75 73

C3= and C4= selectivity (%)

11

88 86 84 82 80 78 76 74 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Cobalt particle size, nm

1,8 1,6 1,4 1,2

Fig. 1. C5+, olefin selectivities vs. Co particle size

Fig. 2. C5+, C3=/C3- and C4= /C4- ratio vs. Co particle size

A volcano type relation for the C5+ selectivity as a function of the Co particle size was obtained as shown in Fig. 1. The results support previous indications of a maximum C5+ selectivity for different Al2O3 supports [2]. The highest C5+ selectivity for the -Al2O3 supported catalysts was obtained at Co particle size of 9-10 nm. According to Fig. 2, the C5+ selectivity varied concurrently with the olefin to paraffin ratio. References: [1] S. Storster, B. Ttdal, J. Walmsley, B.S. Tanem, A. Holmen, J. Catal. 236 (2005) 139. [2] . Borg, P.D.C. Dietzael, A.I. Spjelkavik, S. Eri, J.C. Walmsley, S. Diplas, S.Eri, A. Holmen, E. Rytter, J. Catal. 259 (2008) 161.

P17 Solar Hydrogen Production by Photo-oxidation of Water From Iron Oxide Photoanodes
Alan Kleiman Shwarsctein, Peter C.K.Vesborg, Yidong Hou, Sren Dahl, and Ib Chorkendorff Catalysis for Sustainable Energy Center, Danish Technical University, DK-2800 Lyngby, Denmark High efficiency photoelectrochemical material systems, for the production of hydrogen from water and sunlight, have been proposed and demonstrated;1 unfortunately, the costs of these systems far exceeds any commercially acceptable value for large volume, low value, fuel production. The abundant and inexpensive metal oxides such as TiO2,2 ZnO,3 and WO34 have wide bandgaps and are therefore limited in overall terrestrial solar energy efficiency to less than ~4%. Hematite (-Fe2O3) has several advantages for photoelectrocatalytic chemical conversions using sunlight compared to alternatives. Hematite is an n-type semiconductor with a bandgap of 2-2.2 eV which can capture approximately 40% of the energy in incident sunlight, it is stable inmost electrolytes at pH > 3, and it is abundant, inexpensive, non-toxic and environmentally benign. However, as a Mott-insulator it has several inherent disadvantages which give rise to poor charge transfer and high recombination rates for the photogenerated electrons and holes which limit the efficiency of the pure-phase material. In addition, for water photoelectrolysis, the rate of the oxygen evolution reaction (OER) on hematite is relatively slow. Finally, the energy of the conduction band relative to the redox level of the H2/H+ is too low (~ 0.2 V vs.NHE) to efficiently drive the hydrogen evolution reaction. In order to use hematite as a photocatalyst in large scale solar applications, the factors that limit its performance must be overcome without adding significantly to the cost. Basic studies on model hematite photoelectrodes (Figure 1) with the aims of understanding the rate limiting step for efficient photoelectrochemical hydrogen production on hematite will be discussed. The effect of electrocatalysts deposition on the OER kinetics and doped hematite photoelectrodes for the improvement of the the minority carriers will also be discussed,

Figure 1. Cross section Scanning Electron Microscope image of a sputtered hematite thin film. References 1. Khaselev, O.; Turner, J. A., Science, 280, 425 (1998). 2. Fujishima, A.; Honda, K., Nature, 238, 37 (1972). 3. Jaramillo, T. F.; Baeck, S. H.; Kleiman-Shwarsctein, A.; Choi, K. S.; Stucky, G. D.; McFarland, E. W., J. Com. Chem., 7, 264 (2005).

P18 Characterization of the supported vanadium oxide catalysts by multispectroscopical approach

1

Roman Bulanek1, Michal Setnika1, Pavel imanec Department of Physical Chemistry, University of Pardubice E-mail: libor.capek@upce.cz

Abstract In modern heterogeneous catalysis, supported vanadium oxide catalysts constitute a very important class of catalytic materials. The detailed speciation of vanadium oxide species present on the surface of the support materials is challenging task in the process of the catalyst characterization. These materials attend interest of scientific community due to their unique ability to activate C-H bonds of alkanes at relatively low temperature and role of particular species in catalytic processes is not solved yet. The DR UV-Vis spectroscopy belongs among the most useful experimental methods for the characterization of supported vanadium oxide species. In this contribution, we present newly developed methodology of DR UV-Vis spectra measurement providing more quantitative and qualitative information about VOx speciation. The spectra of the progressively diluted samples of catalysts proved that the KubelkaMunk function values began to be proportional to the concentration of VOx species only for the dilution ratio higher than 50 with retaining constant values of the 0. The spectra of diluted samples consisted of several well separated absorption peaks what is the significant difference from the all previously published UV-Vis spectra of this system. A good separation of absorption bands makes possible to numerically deconvolute spectra to individual absorption bands with high reliability and ascribe theirs presence to abundance of the individual VOx species present on the surface of the support. The results obtained from deconvoluted spectra are consistent with information obtained using the traditional method based on evaluation of the shift of absorption energy edge. Moreover this methodology makes possible to evaluate spectra of samples containing the bulklike V2O5 species whose can not be evaluated by former methodology. The newly developed methodology of DR UV-Vis spectra measurement opens the possibility for the obtaining the quantitative information about abundance of the particular VOx supported species by the simple experimental method. The experimental UV-Vis spectra demonstrated the presence of the several different types of VOx oligomeric species whose abundance was controlled by the catalyst preparation method. Information about vanadium speciation obtained from DR-UV-vis are correlated with information from Raman spectroscopy and H2-TPR characterization. Acknowledgements A financial support of the Grant Agency of the Czech Republic under the project No. P106/10/0196 and Ministry of Education of Czech Republic under project No. MSM 0021627501 is highly acknowledged.

P19 Pechini route in pore: Synthesis of supported catalysts by impregnation and calcination of room-temperature polymerizable metal-complexes
Tiejun Zhao1, Sara Boullosa-Eiras1, Yingda Yu2, De Chen1, Anders Holmen1, Magnus Ronning1 1 Department of Chemical Engineering 2 Department of Material Science and Technology Norwegian University of Science and Technology (NTNU), N-7491, Trondheim, Norway. E-mail: tiejun@chemeng.ntnu.no Impregnation is usually the simplest route for synthesis of supported metals and metal oxides. However, the complexity of the interaction between the metal precursor and the support, solvent evaporation, and phase transformation in the impregnation, drying and calcination treatments may lead to poor dispersion of the active species in the final catalyst [1]. In this contribution, we introduce a novel concept involving the impregnation of an in-situ polymerized metal-complex solution (e.g. Cu(NO3)2, Ce(NO3)3, citric acid, and ethylene glycol) onto the solid supports such as structured carbon nanofibers and alumina powders, where the citric acid can react with metal cations and polymerize with ethylene glycol at room temperature. This is followed by a calcination procedure to remove the polymeric solid and thus giving rise to high-dispersed supported catalysts. We present two catalyst systems: structured carbon nanofibers (SCNFs) supported Cu-CeO2 and Rh/CexZr1-xO2/Al2O3 catalyst. From TEM examination, it is observed that, for 20 wt % Cu-CeO2/SCNFs, an amorphous layer is produced on the surface of the carbon nanofibers after impregnation and drying at room temperature overnight. After calcination in air at 400oC, Cu-CeO2 nanoparticles of 3-5 nm are deposited on the surface of the carbon nanofibers. Formation of these small nanoparticles takes place through a violent reaction between the polymeric solid and oxygen with the help of the remaining nitrate, thus giving rise to a uniform nucleation process on the surface of the carbon nanofibers and preventing the particle size growth. The obtained material shows excellent catalytic performance in preferential oxidation of CO. A similar procedure is used to prepare 0.5 wt%Rh/5-10 wt%CexZr1-xO2/Al2O3 catalysts where a solution containing Ce- or Zr- nitrate, citric acid and ethylene glycol is introduced by impregnation method. It is found that the growth of the particle size and the formation of the thermal-stable but low- surface-area - Al2O3 phase in the nanocomposites are effectively retarded although the samples are calcined at 1100oC for 5 h. Meanwhile, a thermally stable CexZr1-xO2 phase is also produced, implying a synergic stabilization mechanism. The catalytic measurements show a higher conversion and selectivity, and especially a higher stability in methane partial oxidation to syngas compared with Rh/Al2O3 catalyst. This versatile synthesis method can be used to prepare highly dispersed structured or powdered catalysts through impregnation of an in-situ polymeric precursor, followed by calcination to remove the polymeric solid on the support from the reaction between the organic material, oxygen and the nitrate. References [1] A.J. van Dillen, R.J.A.M. Terrde, D.J. Lensveld, J.W. Geus and K.P. de Jong, J. Catal. 216, 257 (2003).

P20 The role of alpha-sites of a Fe-ZSM-5 catalyst in selective catalytic reduction of NOx by ammonia
Dmitry E. Doronkin1, Larisa V. Pirutko2, Evgeny V. Starokon2, Alexandr Yu. Stakheev1, Gennady I. Panov2 1 Zelinsky Institute of Organic Chemistry RAS, 119991, Leninsky Prosp. 47, Moscow, Russia 2 Boreskov Institute of Catalysis SB RAS, 630090, Prosp. Lavrentieva 5, Novosibirsk, Russia E-mail: st@ioc.ac.ru Abstract Iron-containing zeolites (Fe-ZSM-5, Fe-Beta etc.) are known to be effective catalysts for several applications including selective catalytic reduction of NOx by ammonia, N2O decomposition, benzene to phenol oxidation by N2O (alphox) and other processes involving so-called -oxygen [1]. In view of the similarities between active sites for NOx-SCR and -sites facilitating N2O decomposition the question arises if the same species are the active sites for the mentioned processes. To verify the assumption that -sites responsible for zeolite activity in N2O decomposition also determine the zeolite activity in NH3deNOx we obtained two series of Fe-ZSM-5 samples containing 0.03-2 wt.% Fe with quantified -sites concentration (-sites quantification procedure is given in [1]). The catalysts were studied in the selective catalytic reduction of NOx by NH3. It is found that high-temperature activation leads to the increase in -sites concentration together with increase in Fe-ZSM-5 activity in SCR of NOx by NH3. However detailed study revealed that activity of Fe-ZSM-5 catalysts in NH3-deNOx is determined not only by -sites concentration but rather by concentration of several types of Fe species in the catalyst. Still the high-temperature activation procedures can be useful for preparation of Fe-ZSM-5 catalysts for NH3-deNOx in several cases. One of them is that activation facilitates transfer of framework Fe to extraframework positions which is necessary for zeolites where Fe was introduced during zeolite synthesis. Another function of activation is that it facilitates deactivation of Fe oxide phase (e.g. by destruction or decreasing its surface area) in Fe-ZSM-5 catalysts with high Fe loadings. Therefore unselective oxidation of ammonia at high temperatures is hindered and high selectivity of NH3-deNOx can be achieved. The latter was verified by experiments of ammonia oxidation over given samples. D. Doronkin is grateful to Haldor Topse A/S for financial support in the framework of Ph.D. student support programme. This work was supported (regarding synthesis and characterization of iron-containing zeolites) by Federal agency on science and innovations (State contract 02.740.11.0147). References [1] K.A. Dubkov, N.S. Ovanesyan, A.A. Shteinman, E.V. Starokon, and G.I. Panov, J. Catal. 207, 341 (2002).

P21 Hydroisomerization of Fischer-Tropsch wax on Pt/AlSBA-15 and Pt/SAPO-11 catalysts

Gyrgy Plczmann1, Jzsef Valyon2, Jen Hancsk1 University of Pannonia, Department of Hydrocarbon and Coal Processing 2 Chemical Research Center, Institute of Chemistry, Hungarian Academy of Sciences E-mail: hancsokj@almos.uni-pannon.hu
1

Abstract Because of the more serious problems with the environment (e.g. greenhouse effect) and with the crude oil supply (e.g. import dependence) the use of fuels and lubricants produced from renewable feedstocks has come to the front nowadays. The products (fuels and base oils) which can be produced from FischerTropsch wax are of high quality and they are environmentally friendly. Accordingly it is very important to develop a catalytic system (identification of the proper catalysts and advantageous process parameters) that can be applied to produce the target product (mixture of gas oil and base oil) with selective isomerization (skeletal arrangement) and with high isoparaffin selectivity [1-2]. The isomerization of high molecular weight n-paraffins can be effectively carried out on bifunctional catalysts. There are only a few indications about the application of metal catalysts on mesoporous carrier in the literature [3,4]. Consequently our objective was to investigate a Pt/AlSBA-15 catalyst which has not been investigated in detail in this reaction system yet, compared with a Pt/SAPO-11 catalyst which was earlier applied for isomerization of high molecular weight n-paraffins [3]. From the catalysts with different carriers the best liquid product yields were gained on the Pt/SAPO-11 catalyst, but until 325 C this value was above 95% in every case on the Pt/SBA-15 catalyst, too. In case of both catalysts in the gas products mainly branched isobutane was identified, which indicated that the cracking enacted partly after the isomerization reactions. We concluded that the isoparaffin content of the liquid products was much higher in case of Pt/AlSBA-15 catalyst at similar parameters. Based on the isoparaffin contents of the different fractions produced on Pt/AlSBA-15 it can be concluded that at advantageous process parameter combinations (T=300-325 C, P=40-70 bar, LHSV=1.0-2.0 h-1 / T=275-300 C, P=40-70 bar, LHSV=1.0-2.0 h-1) the catalyst was applicable to produce C11-C20 and C21C30 fractions with high isoparaffin content (64.5-86.6% / 35.1-59.7%) with adequate yields (28.9-35.6% / 45.2-57.8%). To summarize it, it was concluded that the catalysts with AlSBA-15 carrier showed the better results in the production of gas oil and base oil fractions with high isoparaffin content from Fischer-Tropsch wax. The selectivity of the target product fractions was high, and based on these facts the selective isomerization of the Fischer-Tropsch wax is a new application area of the Pt/AlSBA-15 catalyst. References [1] Zhou, Z., Zhang, Y., Tierney, J.W.: Producing fuels from Fischer-Tropsch waxes, PTQ, 2004, 4, 137-143. [2] C. Bouchy, G. Hastoy, E. Guillon, J.A. Martens: Fischer-Tropsch Waxes Upgrading via Hydrocracking and Selective Hydroisomerization, Oil & Gas Science and Technology, 2009, 64, 91-112. [3] Deldari, H.: Suitable catalysts for hydroisomerization of long-chain normal paraffins, Appl. Catal. A: General, 2005, 293, 1-10. [4] Rosetti, I., Gambaro, C., Calemma, V.: Hydrocracking of long chain linear paraffins, Chemical Engineering Journal, 2008, 154, 295-301.

P22
95

Mo MAS NMR of MoS2 Reveals Precise 95Mo Anisotropic Parameters from the Central and Satellite Transitions for Characterizing Its Structure

Hans J. Jakobsen1, Henrik Bildse1, Jrgen Skibsted1, Michael Brorson2 and Kjeld Schaumburg3 Instrument Centre for Solid-State NMR Spectroscopy, Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark 2 Haldor Topse A/S, Nymllevej 55, DK-2800 Lyngby, Denmark 3 CISMI, Roskilde University, Universitetsvej 1, DK-4000 Roskilde, Denmark E-mail: hja@chem.au.dk

Abstract Molybdenum disulfide, MoS2, or molybdenite as it is called in its mineral form, is the primary source for the metal molybdenum and its compounds. MoS2 itself has industrial applications as solid lubricant, due to its layered (graphite-like) crystal structure, and as the active component in heterogeneous hydrodesulfurization catalysts. In the latter case nanosized MoS2 crystals are usually dispersed on highsurface area -alumina and promoted with Co or Ni in order to boost the catalytic activity. Although several attempts have been made, none of the investigations conducted so far have presented a complete solidstate 95Mo NMR study of MoS2 that results in precise values for both the 95Mo quadrupole coupling and chemical shift anisotropy (CSA) parameters. The lack of a solid-state 95Mo NMR spectrum that allows a complete characterization of MoS2 has prompted us to undertake a wide bandwidth 95Mo MAS NMR study. We here take full advantage of the experience gained from our earlier wideband low- MAS NMR studies on 14N and 33S MAS NMR. The present study reports precise 95 values for the 95Mo (CQ, Q) and (, , iso) parameters in MoS2, as Figure 1. MoS2: Mo MAS NMR determined from natural abundance 95Mo MAS NMR of a MoS2 spectra (14.1 T). (a) Experiment. (b) Optimized simulated fit of spectrum mineral sample on a mid-field (14.1 T) spectrometer. These data are of (a) showing the CT and all STs. The interest not only in relation to the well-known layered structure of insets show expansions for the CT. MoS2, but also as benchmark data in future applications of solid-state 95 Mo NMR experiments for characterization of MoS2 species in various fields of materials chemistry, e.g., for hydrodesulfurization catalysts. An experimental natural abundance 95Mo MAS NMR spectrum of the MoS2 mineral (Fig. 1a) clearly shows groups of 95Mo resonances for both the +1/2 1/2 CT and the two 3/2 1/2 inner satellite transitions (STs) for this spin I = 5/2 quadrupole. An optimized fit to the experimental spectrum in Fig. 1a is displayed in Fig. 1b for the CT and all STs and shows an excellent agreement with the experimental spectrum. While the extracted 95Mo quadrupole coupling, CQ = 3.61 MHz, is fairly large compared to earlier reported values for 95Mo, the 95Mo CSA, = 1018 ppm, is the largest observed so far in 95Mo NMR. In addition, the optimized fit produces asymmetry parameters = Q = 0, in full agreement with the trigonal prismatic-site symmetry of Mo in the structure of MoS2.

P23 Hydrogen Produced by Ru/(CuAg)xIn2xZn2(1-2x)S2 Photocatalysts via Water-Splitting Reaction

1,2

Ien-Whei Chen1, Chih-Hao Tan2, Chung-Yen Wu3 Department of Chemical Engineering, Tatung University,Taipei, Taiwan, R. O. C. E-mail: iwchen@ttu.edu.tw

Abstract Hydrogen production under visible light irradiative water-splitting reaction on Ru/(CuAg)xIn2xZn2(1-2x)S2 photocatalysts were investigated in this study. The photocatalysts were prepared with the various proportions of Cu2S, Ag2Sx, In2S3 and ZnS precursors at different reaction temperatures. The flux method was proceeded by adding of Na2Sx into precursors as the flux at desired preparation temperature for 1 hour. The prepared (CuAg)xIn2xZn2(1-2x)S2 were then loaded with Ru to obtain the Ru/(CuAg)xIn2xZn2(1-2x)S2 photocatalysts. The photocatalysts were characterized by means of X-ray diffraction (XRD), UV-Vis spectrophotometer (UV-Vis), scanning electronic microscope (SEM) and energy dispersive spectrometer (EDS). It could be seen from XRD results that the photocatalysts obtained under 600 preparation possessed the best crystalline structure. The structure of (CuAg)xIn2xZn2(1-2x)S2 photocatalysts transformed from the crystalline of two mixing phases of Wuritzetype and Zinc-blend type structures to single Chalcopyrite structure with the increase of x. From UVVis results, it could be seen that the greatest red shift of the absorption band edges appears at x=0.25 for (CuAg)xIn2xZn2(1-2x)S2 photocatalysts. From SEM results, (CuAg)xIn2xZn2(1-2x)S2 photocatalysts prepared at 600 possessed small and uniform particle sizes. However, the particle sizes increased with increasing of x in (CuAg)xIn2xZn2(1-2x)S2 photocatalysts. The photocatalytic water-splitting reaction for hydrogen production was carried out in a batch reactor under the irradiation of the 450W metal halide lamp. The hydrogen evolution rate of 586 mole/h was obtained by Ru(0.5wt%)/(CuAg)0.25In0.5ZnS2 photocatalyst prepared at 600 and adding of Na2S(0.25M)/K2SO3(0.35M) sacrificial reagent. References [1] Kudo A., Tsuji I., Kato H., Kobayashi H., J. of Physics and Chemistry B, 109 7323 (2005). [2] Schorr S., Riede V., Spemannb D., Doering Th., J. of Alloys and Compounds, 414 26 (2006). [3] Kudo, A., International Journal of Hydrogen Energy, 31 197 (2006). [4] Hunger, R., Pett enkofer, C., Scheer, R., Surf. Sci., 477 76 (2001). [5] Kanatzidis M. G., Chem. Material., 2 353 (1990). [6] Yang H. H., Guo L. J., Yan W., H. T. Liu, J. of Catal. B, 159 1305 (2006).

P24 Characterization of the active sites in spent and regenerated ZSM-5 catalysts by 1H, 13 C, 27Al, and 29Si MAS NMR spectroscopy
Sren Srensen1, Henrik Fordsmand2, Ton V. W. Janssens2, Pablo Beato2, Hans J. Jakobsen1, and Jrgen Skibsted1 1 Instrument Centre for Solid-State NMR Spectroscopy and Interdisciplinary Nanoscience Center (iNANO), Department of Chemistry, Aarhus University, 8000 C Aarhus, Denmark. 2 Haldor Topse A/S, Nymllevej 55, DK-2800 Kgs. Lyngby, Denmark. E-mail: soerens@phys.au.dk Abstract Highly silicious ZSM-5 is one of the most important zeolite catalysts, used in a range of different industrial applications. For example, ZSM-5 with Si/Al ratios of 20 100 can be used in the conversion of methanol to gasoline (MTG) where the zeolite typically operates at 300 - 400 C. The ZSM-5 material is gradually deactivated during this process as a result of the formation of coke both on the outer surface of the zeolite crystals and within the pore structures. The deactivation by coke formation is reversible, as it can be removed from the zeolite by burning the material at 500 600 oC. On the other hand, deactivation of zeolites by dealumination of the zeolite framework is permanent and cannot be recovered by regeneration. This work utilizes 1H, 13C, 27Al and 29Si MAS NMR to investigate the nature of coke in spent ZSM-5 zeolites from the MTG process as well as the catalytically active AlO(H)Si Brnsted sites in spent zeolites before and after different regeneration procedures. The 13C MAS NMR spectrum of the spent zeolite is dominated by a broad resonance from aromatic carbon atoms (110 150 ppm) while only a minor peak, constituting 13% of the total intensity, is observed for aliphatic carbons (10 30 ppm). The 27 Al MAS NMR spectrum (14.1 T) of the fresh ZSM-5 zeolite contains two peaks for Al in tetrahedral coordination at 55.8 and 53.4 ppm. The peaks could be assigned to a second-order quadrupolar lineshape for a single structural AlO4 site. However, 27Al MQMAS spectra recorded at 9.4 and 14.1 T clearly reveal that the zeolite contains two distinct AlO4 sites. In contrast, the spent zeolite shows a single AlO4 resonance in the 27Al MAS spectrum at a slightly lower chemical shift as compared to the Al sites in the original material. Moreover, broad resonances from either a distorted AlO4 site or penta-coordinated Al species are observed in the range 30 50 ppm along with a minor resonance from Al in octahedral coordination. After regeneration by oxidation of the coke, the 27Al MAS NMR spectra again reveal the two AlO4 resonances but also show that the materials still contain a significant amount of distorted AlO4/AlO5 and octahedrally coordinated Al. Thus, these spectra show that dealumination of the zeolite framework takes place during the regeneration processes. Very-high speed 1H MAS NMR spectra, recorded with a spinning speed of R = 40.0 kHz using 1.6 mm rotors, give additional information about the coke that is left in the zeolites after regeneration, thereby supplementing the rather insensitive 13C MAS NMR experiments. Generally, the 1H MAS spectra of the spent and regenerated zeolites are dominated by resonances from water absorbed in the structure and framework hydroxyl groups. Nevertheless, 1H resonances at 6.8 8.0 ppm and 2.7 ppm are clearly visible, which are assigned to aromatic CH and aliphatic CH species in the coke that is left in the zeolite after regeneration.

P25 Microwave irradiated Pd/Al2O3 catalysts for N2O decomposition

Siva Sankar Reddy Putluru1, N. Lingaiah2, P.S. Sai Prasad*2. 1 Department of Chemical Engineering, Technical University of Denmark, Denmark 2 Catalysis Division, Indian Institute of Chemical Technology, Hyderabad, India E-mail: saiprasad@iict.res.in Abstract 5 wt.% alumina-supported palladium catalysts were prepared by deposition precipitation (DP) and impregnation (IMP) methods adopting conventional heating and microwave irradiation (MW) and tested for N2O decomposition. All the catalysts were well characterized with CO chemisorption, XRD, TPR and In-situ DRIFTS adsorption methods. Pt, Ru, Rh and Pd catalysts prepared by conventional method have been mostly used in commercial processes for N2O decomposition [1-2]. However, catalysts prepared by novel methods are necessary to modify the active site geometry in order to achieve higher activity. In recent years there have been many reports that contributed to the positive role of microwave irradiation in the synthesis of catalysts [2]. From Figure 1 it can be observed that each catalyst follows its own path to reach 100% N2O conversion. The activity measured at 350 oC varies in the order DP MW>IMP MW>DP>IMP. From Table 1 it is clear that the particle size of Pd changes with the method of preparation and microwave irradiation affords formation of a favorable bulk Pd particle that leads to higher N2O decomposition.

Figure 1: Activity profiles of Pd/Al2O3 catalysts with reaction temperature. Reaction Conditions: 5000 ppm N2O in He; space velocity of (15000 h-1). Table 1: CO chemisorption results of Pd/Al2O3 catalysts
Catalyst CO uptake (Ncc/g) IMP 0.52 DP 0.54 IMP MW 0.48 DP MW 0.36 Dispersion (%) 4.9 5.2 4.6 3.4 Specific metal area (m2 / g) 1.10 1.13 1.01 0.75 Particle size (nm) 22.4 21.8 24.3 32.9

References [1] P.S.S Reddy, N. Pasha,N. Lingaiah, P.S. Sai Prasad, Catal.Commun 8, 1046 (2007). [2] P.S.S Reddy, N. Seshu Babu, P.S. Sai Prasad, Catal.Commun 9, 2303 (2008).

P26 Investigation of the effect of oxygenic compounds on the isomerization of bioparaffins over Pt/SAPO-11 catalyst
Hancsk, J., Kovcs, S., Plczmann, Gy., Kasza T. Department of MOL Hydrocarbon and Coal Processing, Pannon University P.O. Box 158., H-8201, Veszprm, Hungary E-mail: hancsokj@almos.uni-pannon.hu The industrial development and the population growth are leading to increasing energy demand, consequently the role of bio-fuels are becoming more acute because of their environmental advantage. The mainly normal paraffin containing mixtures produced from different triglycerides (conventional and ennobled vegetable oil, used cooking oils and fats, etc.) have high cetane number and excellent performance properties, but their freezing points are high (+15 +32C), consequently this feature is need to be improved. For this the most suitable process is the isomerization, because among paraffins with the same carbon number, the branched paraffins have a lower freezing point by 10-40C, relative to normal paraffins, but at the same time the cetane number decrease is only 10-20 unit. During the production of these mixtures the products always contain some other components like oxygenic compounds (carboxyl acids, esters, etc.) in function of the operational parameters. The minimization of the quantity of these oxygenic compounds is expedient which could be realised by increasing the severity of the operational parameters (temperature, pressure, etc.), which not only increases significantly the operational cost, but it causes the decrease of the product yield because of the increasing rate of cracking reactions, which is disadvantageous. Up to now in the topic of isomerization of mixtures which contain mainly heptadecane and octadecane produced by the catalytic hydrogenation of vegetable oils there have been only a few publications. [1-3]. Previously mainly the isomerization of lower carbon number paraffins (n-C8 n-C12) was investigated. In case of n-C16 n-C24 mainly high purity model compounds were used in small concentration (1-40%) in the isomerization experiments [1]. The catalytic conversion of these paraffins is practical to be carried out over catalyst having high isomerization activity to reach favourable yield. Such high isomer selective catalysts are the 10 member ring zeolites (ZSM-22, ZSM-23, etc.) and different zeolit analogs (SAPO-11, SAPO-31, SAPO-41, etc.) with different noble metal content. Unfortunately these high isomerization activity catalysts are sensible to oxygenic compounds (the water generated by the hydrogenation of oxygenic compounds destroys the structure of the zeolite). The aim of our research work was the investigation of the effects of oxygenic compounds (oleic acid, methyl ester mixture, etc.) generated during the hydrogenation of vegetable oils on the isomerization of 0-5% oxygenic compounds containing mixtures over Pt/SAPO-11 catalyst in function of the operational parameters. According to the experimental results it was concluded that in case of mixtures containing 5% oleic acid and/or esters the isomerization activity and the lifetime of the catalyst decreased significantly. References [1] [2] [3] Marion C. Claude, et al., Journal of Catalysis 203, 213231 (2001) Hancsk, J. et al., Microporous and Mesoporous Materials, 2007, 101(1-2), 148-152. Hancsk, J. et al., Stud. in Surf. Sci. & Cat. 170 B, 2007, 170, 1605-1610.

P27 The effect of sulphur and water treatments on the performance of Pd/-zeolite diesel oxidation catalysts
Tanja Kolli1, Mika Huuhtanen1, Tomi Kanerva2, Minnamari Vippola2, Kauko Kallinen3, Toivo Lepist2, Jouko Lahtinen4, and Riitta L. Keiski1 1 Dept. Process and Environmental Eng. POB 4300, FI-90014 University of Oulu, Finland 2 Tampere Univ. of Tech., Dept. of Materials Science, POB 589, FI-33101 Tampere, Finland 3 Ecocat Oy, Typpitie 1, FI-90620 Oulu, Finland 4 Aalto University, Dept. of Applied Physics, POB 11100, FI-00076 Aalto, Finland. E-mail: tanja.kolli@oulu.fi Abstract The diesel oxidation catalysts (DOCs) promote the total oxidation of carbon monoxide, gaseous unburned hydrocarbons, and the soluble organic fraction of particulates [1]. Pt-containing ZSM-5 catalysts have demonstrated their effectiveness in reducing NOx with hydrocarbons in diesel exhaust gas catalysis with high oxygen content [2]. However, zeolite-based diesel catalysts are also deactivating both at low and high temperatures especially in moist conditions as well as in the presence of poisons, such as sulphur [3]. In this study, the effects of sulphur and water treatments on the Pd/-zeolite catalysts were investigated. Fresh and SO2- (S-), SO2+H2O- (SW-) and H2O- (W-) treated 4 wt-% Pd/-zeolite catalysts were studied. The fresh samples were provided by Ecocat Oy. The S-, SW-, and W-treatments were done as described in our previous study [4]. The following analyses are done to find out the effect of S-, SW-, and W- treatments: X-ray fluorescence (XRF), specific surface area (BET), catalytic activity, structural (TEM) and surface analysis (XPS). According to XRF and BET results, S- and SW-treatments have a deactivating effect on the Pd/-zeolite catalysts. Based on the activity tests, the S-treated Pd/-zeolite was deactivating more than the other studied catalysts. TEM-results by Kanerva et al. [5] revealed increased Pd particle sizes for the S-treated Pd/-zeolite catalyst. Both the SW- and W-treated catalysts showed better activity to oxidize CO and C3H6 than the fresh catalyst. CO and surface OH-groups react very easily at low temperatures to carbonates on the commercial TWC catalysts [6]. This effect could explain the lower light-off temperatures of CO over the W- and SW-treated Pd/-zeolite catalysts than over the fresh catalyst. References [1] [2] [3] [4] [5] [6] F. Gabello Galisteo, R. Mariscal, M. Lpez Granados, M.D. Zarfa Poves, L.J.G. Fierro, V. Krger, R.L. Keiski, Appl. Catal. B Environ. 72, 272 (2007). M. Huuhtanen. Dissertation thesis, University of Oulu, Oulu, 2006. V. Krger, T. Kanerva, U. Lassi, K. Rahkamaa-Tolonen, T. Lepist, R.L. Keiski, Top. Catal. 4243, 433 (2007). T. Kolli, T.Kanerva, P. Lappalainen, M. Huuhtanen, M. Vippola, T, Kinnunen, K. Kallinen, T. Lepist, J. Lahtinen, and R.L. Keiski, Top. Catal. 52, 2025 (2009). T. Kanerva, T. Kolli, K. Kallinen, T. Kinnunen, M. Vippola, T. Lepist, R. L. Keiski, SCANDEM conference, 2 June to 4 June 2008, Lyngby, Denmark. H.J. Kwon, J.H. Baik, Y.T. Kwon, I.-S. Nam, S.H. Oh, Chem. Eng. J. 141, 194 (2008).

P28 TiO2 on aligned CNF substrates for photocatalytic water splitting

Asmira Delic, Estelle Vanhaecke, Magnus Rnning Department of Chemical Engineering, NTNU, N-7491 Trondheim, Norway E-mail: ronning@chemeng.ntnu.no Abstract Photocatalytic water splitting is an environmentally clean alternative to hydrogen production from fossil fuels. The most appropriate semiconductor for photocatalytic reactions is considered to be TiO2. Currently there are two major challenges regarding the use of TiO2 for photocatalytic water splitting. The first problem is deactivation through recombination of the photogenerated electron-hole pairs. The second problem is that the material is active upon UV radiation and not visible light, which is the main part of the solar spectrum. A promising approach for suppressing the recombination of electron-hole pairs is to couple TiO2 with carbon-based materials. The synergetic effects depend on the type of carbon material as well as the synthesis route of the TiO2carbon composites [1, 2]. In this work we explore the structure and function of different TiO2/CNT ratios, different types of carbon nanotubes (CNT) and different location of TiO2, i.e. outside and inside the CNT. The CNT were prepared by CVD on carbon support with subsequent decoration of the tubes by TiO2. TiO2 was prepared by sol-gel and by hydrolysis of TiCl4. The samples were characterized by TEM, SEM, XRD, BET, TGA and Raman spectroscopy. The photocatalytic activities of the different samples were evaluated by separate production of H2 and O2 in water splitting in a photoelectrochemical reactor (PEC), as first conceptualized by Centi et.al [3]. For comparison, a sample consisting of a TiO2 dense film instead of TiO2/CNT was used. The diameter and length of the synthesized CNT was 20-50 nm and ~15 m, respectively. The photocatalytic activity of TiO2/CNT is estimated to increase significantly compared to TiO2 dense film. The rate of hydrogen formation is assumed to be more efficient than previous reports as the reactor configuration allows separation of generated H2 and O2. References 1. Y. Ou, J. Lin, S. Fang, D. Liao, Chem. Phys. Lett. 429 (2006) 199203. 2. J.L. Faria, W. Wang, Carbon materials in photocatalysis, in: P. Serp, J.L. Figueiredo (Eds.), Carbon Materials for Catalysis, Wiley, New Jersey, 2009, pp. 481506. 3. G. Centi, S. Perathoner, Catalysis Today 138 (2008) 6976.

P29 Improvement of photoelectrochemical hydrogen generation at p-type silicon by surface modification with noble metal free catalyst
Yidong Hou1, Billie L. Abrams1, Peter C.K. Vesborg1, Konrad Herbst2, Christian Damsgaard3, Su-Il In1, Alan Kleiman-Shwarsctein1, Ole Hansen3, Ib Chorkendorff1* 1 Center for Individual Nanoparticle Functionality (CINF), Department of Physics, Technical University of Denmark, Dk-2800 Kongens Lyngby, Denmark 2 Haldor Topse A/S, Nymllevej 55, Dk-2800 Kongens Lyngby, Denmark 3 Department of Micro and Nanotechnology, Technical University of Denmark, Dk-2800 Kongens Lyngby, Denmark E-mail: ibchork@fysik.dtu.dk Abstract Photoelectrochemical hydrogen evolution from water at semiconductor has been regarded as one of the promising techniques for the conversion of sunlight into hydrogen as a clean and renewable source of energy [1]. A variety of semiconductors, such as TiO2, TaON, GaN:ZnO, GaP, GaAs and Si, have been proposed as the materials for the photo-electrodes. Among of them, Silicon (Si) is an interesting candidate as a light absorbing material due to the low band gap (1.1 eV) enabling effective utilization of the visible and IR light from the sun. Additionally, it is very abundant and thus inexpensive. However, Si alone has rather poor hydrogen evolution kinetics. The strategy has been proposed to catalyze the hydrogen evolution by loading electro-catalyst onto Si surface. For example, deposition of noble metal islets (such as Pt) on p-Si had a profound effect on its activity [2]. Unfortunately, Pt is an expensive and rare material and the cost of such systems is far too high for large scale production. Our previous studies demonstrated that the MoXSy are quite active electrocataysts for hydrogen evolution [3, 4]. The present work shows that p-Si modified with this type of electro-catalyst (noble metal free) exhibits significant improvement for photoelectrochemical hydrogen evolution compared to the naked p-Si. The potential shift between modified p-Si and naked p-Si at a current density of 1mA/cm2 was about 0.63 V shown in Figure 1.
0

0.63 V

Current (mA/cm )

-1

-2

naked p-Si
-3

modified p-Si

-4 -1,2

-1,0

-0,8

-0,6

-0,4

-0,2

0,0

0,2

Figure1: Potentiodynamic runs on the photoelectrodes (475-525 nm, 8.8 mW/cm2, 0.1 M HClO4) References [1] J. Nowotny et al, Int. J. Hydrogen Enery, 27, 991(2002). [2] M. S. Wrighton et al, J. Am. Chem. Soc., 104, 467(1982) [3] I. Chorkendorff et al, Science, 317, 100(2007) [4] I. Chorkendorff et al, J. Phys. Chem. C, 112, 17492(2008)

Potential (V vs. RHE)

P30 Electrochemical Fixation of Carbon Dioxide

Wei Tang, Sofia Varela, Sren Dahl,* Ib Chorkendorff Center for Individual Nanoparticle Functionality and Department of Physics, Technical University of Denmark, Lyngby, Denmark, DK-2800 E-mail: Sren.Dahl@fysik.dtu.dk Abstract The electrochemical conversion of CO2 was investigated with the goal to improve the yield of desirable molecules and control the product selectivity into products, such as methanol, methane, CO, and ethylene at ambient conditions. Among the studied metals in the past,1-4 copper is the only electrocatalyst capable of effectively producing hydrocarbons, instead of producing hydrogen by reacting with the aqueous electrolyte. To reveal the electrochemical route of CO2 electro-reduction, the distribution of reaction products was analyzed as a function of applied bias. In addition, the catalytic performance of copper was shown significantly affected by surface morphology, pretreatment, the nature of the cation in the aqueous electrolyte, and the pH of electrolyte. HER
0 -2
I / mA

1 0
I / mA

Cu after N2 Cu after CO2

-4 -6 -8

-1 -2 -3

-10 -1.5 -1.0

CO2 reductio n at 0.65 V

-0.5 0.0 Ewe/V vs. NHE 0.5

CO2 reducti on at 0.75V

-1.0 -0.5 0.0 Ewe/V vs. NHE 0.5

-1.5

Figure: Cyclic voltammograms of Cu electrode (a) in 0.1 M potassium phosphate (b) in 0.1M potassium bicarbonate. The electrolyte was saturated with nitrogen (black line), and carbon dioxide (red line). The pH values in both electrolytes are 8.0. The arrows indicate the direction of scanning References [1] Y. Hori, In Modern Aspects of Electrochemistry 89-189 (2008). [2] Y. Hori, H. Konishi, T. Futamura, A. Murata, O. Koga, H. Sakurai, K. Oguma, Electrochim. Acta 50, 5354-5369 (2005). [3] Y. Hori, A. Murata, R. Takahashi, J. Chem. Soc., Faraday Trans. I 85, 2309-2326 (1989). [4] Y. Hori, I. Takahashi, O. Koga, N. Hoshi, J. Phys. Chem. B 106, 15-17 (2002).

P31 Methane Oxidation on Gold A combined Microreactor and DFT Study

1

Guido Walther1, Tao Jiang2, Duncan J. Mowbray2 and Sebastian Horch3 Leibniz Institute for Catalysis, Albert-Einstein-Strae 29 A, D18055 Rostock, Germany 2 CAMD, Department of Physics, DTU, DK2800 Kgs. Lyngby, Denmark 3 CINF, Department of Physics, DTU, DK2800 Kgs. Lyngby, Denmark E-mail: Guido.Walther@catalysis.de

Abstract Partial CH4 oxidation has for long time been a dream reaction that could help to solve a range of severe, high impact problems. One of the catalysts that seemed very promising in that context is nanoparticulate gold. Unfortunately, mostly full combustion is observed. In order to avoid this, one needs to hinder CO oxidation, which represents the final part of the reaction pathway of CH4 oxidation on Au. This seems, indeed, to be possible: In recent activity studies we found that whereas the activation energy for CO oxidation is independent of the cluster size for small clusters (r 5 nm) the corresponding activation energy for CH4 does decrease with decreasing cluster size. Thus a critical cluster size below which partial CH4 oxidation is indeed possible might exist. To elucidate this further more, density functional theory calculations are being performed. A previous theoretical study using DFT shows that the Sabatier rate of CO oxidation on Au 55 atoms cluster is very close to that on defect sites of Au surfaces, which agrees well with our experimental results. For CH4 oxidation, the first dehydrogenation step is considered as the rate determine step, hence it is important to study the reactivity change of this reaction on Au catalysts with different sizes. The reaction rate of this first dehydrogenation step of CH4 on a Au 55 atoms cluster and a Au{532} surface (which is used to simulate a defect site of large Au clusters) is being calculated and preliminary results are presented.

P32 Production of biocomponent containing gas oil with the coprocessing of vegetable oil-gas oil mixture
Csaba Tth1, Pter Baladincz1, Jen Hancsk1 1 University of Pannonia, Department of MOL Hydrocarbon and Coal Processing E-mail: tothcs@almos.uni-pannon.hu Abstract Long-term forecasts show a tendency toward increasing energy consumption thus the use of engine fuels increases because of the growing population and its increasing mobilization. For these reasons, the production and use of biofuels is a current problem. To meet the requirements of the EU the biodiesel (FAME) is used as blending component in the gas oils. The blended biodiesel has more unfavorable properties (bad thermal and oxidation stability, sensitivity to hydrolysis, poor cold flow properties, etc.), so a lot of research began to replace it. One of the possible solutions is the heterogeneous catalityc hydrogenation of the vegetable oils (triglycerides), during which the so-called bio gas oil (mixture of i-, and n-paraffins in gas oil boiling point range) can be produced. The bio gas oil is a full value bio blending component, its quantity is not limited by the current gas oil standard EN 590:2009 against the biodiesel. The triglycerides can not only be hydrogenated alone for production of biofuel, but mixed with distillation gas oils - or others before quality upgrading in one catalytic step. To the examination of this we used in the experiments mild hydrocracking gas oil with 10-20% sunflower oil-, high aromatic- (52%) and low sulfur (<100 mg/kg) content. During the experiments we changed the sulfur content of the feedstocks with mixing of a model compound (dibenzothiophene - one of the most difficult hydrodesulphurable molecule in gas oils), and studied the effect of sulfur on the transformation of triglycerides. Expedient composition NiMo/Al2O3 catalyst was used. The combination of process parameters (T=300-380 C, P=80 bar, LHSV=1.0 h-1, H2/HC=600 Nm3/m3) were the same in case of each feedstock. We investigated the impact of the process parameters and the sulfur content of the feedstocks on the yield, the physical-, chemical- and application properties of the main product. On the basis of the results we obtained that the reactions of both of the conversion of vegetable oil (saturation of olefinic double bonds, hydrodeoxigenation) and the gas oil quality improvement reactions (heteroatom removal, reduction of aromatic content) took place. Under the usage of favorable process parameters (360-380 C, P=80 bar, LHSV=1.0 h-1, H2/HC=600 Nm3/m3 and 10-20% vegetable oil content of feedstock) the main properties - except for the CFPP value - of the high-yield produced product satisfy the requirements of standard EN 590:2009. Using model sulfur compound we found that the mixing of vegetable oil reduces the efficiency of hydrodesulphurization compared to the pure gas oil feedstock, because the heteroatom removal reactions took place on same active centers. Based on the results we concluded that an existing hydrogenation plant with a slight modification may be suitable for the processing of vegetable oil and gas oil mixtures. In a single step it can be achieved to improve the quality of the gas oil part (reduction of sulfur-, nitrogen-, aromatic content) and the conversion of vegetable oil part to n-and i-paraffins.

P33 Hydrogenation of the aromatics and olefinic hydrocarbons of the FCC gasoline in the condition of deep desulphurisation
1

J. Hancsk1, G. Marsi1, D. Kall2 University of Pannonia, MOL Department of Hydrocarbon and Coal Processing, H-8200 Veszprm, Egyetem str.10, Hungary 2 Hungarian Academy of Sciences, Chemical Research Center, Budapest, Pusztaszeri str. E-mail: hancsokj@almos.uni-pannon.hu

Abstract The sulphur content of the FCC gasoline which comes from the fluid catalytic cracking of the heavy hydrocarbon distillates is generally 30-200 mg/kg. Therefore this gasoline could be used for the production of gasolines with lower sulphur content than the 10mg/kg only after a deep desulphurization. The most commonly applied technology is the catalytic desulphurization. Through the desulphurization the partial saturation of both the olefins and aromatic hydrocarbons as a function of applied process parameters and catalysts enacts. This effect decreases the octane number of the product, because the octane number of the formed linear and cycloparaffins are lower than that of the olefin and aromatic hydrocarbons (except the dibranched paraffins: 2,3-dimethyl-butane). The objectives of our research work were the investigation of hydrogenating reactions of olefin and aromatic hydrocarbons on different catalysts and the possibilities of the octane number compensation in the highly effective desulphurization. On conventional and new composition CoMo/Al2O3, PtPd/USY/Al2O3 and Pt/HMOR/Al2O3 catalysts different sulphur containing FCC naphtha reactions of catalytic conversion (desulfurization, denitrogenation, olefin and aromatic hydrogenation and isomerization) was studied under the following process parameters: T=200-330C, p=20-40bar, LHSV=1.0-3.0h-1 and H2/hydrocarbon ratio 150-350Nm3. From the results it was concluded that with the application of any individual catalyst the olefin hydrogenation was between 15-60%, near the desulphurization even the aromatic saturation on higher temperature and pressure. These effects caused 3-8 units decrease in the octane number. During the investigation of the simultaneous application of catalysts, both the hydrogenation reactions and isomerization of paraffin hydrocarbons were observed on the modern CoMo/Al2O3+Pt,Pd/USY+Pt/H-MOR (expedient composition: relatively high ratio of acid and metal active sites) catalyst system. The formed high octane number isoparaffins partly compensate the octane number decrement (1.0-2.5), though the olefin and aromatic content of the products decreased. This effect has further advantages in the production of environmental friendly gasoline (lower aromatic and olefin content). References: [1] Hancsk, J., Magyar, Sz., Holl, A., Thernesz, A.: Investigation of the upgrading of FCC gasolines on Pt-Pd/USY catalyst, 19th World Petroleum Congress, Spanyolorszg, Madrid, 2008. June 29. July 3., In Proceedings (ISBN 978-0-85293-499-9), B2/F9-P5. [2] Elshout, R.V., Bains C.S., Hydrocarbon Engineering, 2005, 10(2), 71-76 [3] Blanchard, L., Ziebarth, M., Dougan, T., Davison, G., Hydrocarbon Engineering, 2007, 12(3), 31-35.

P34 Titanium dioxide coating on polyurethane surfaces

Ritva Lenkkeri, Kaisu Ainassaari, Riitta L. Keiski Univ. of Oulu, Dept. of Proc. and Env. Eng., POB 4300, FIN 90014 University of Oulu E-mail: ritva.lenkkeri@oulu.fi Abstract Titanium dioxide is a common catalyst in the photocatalytic methods because of its good activity and non-toxicity. It has been used mostly in water and gas purification processes but also in the prevention of the fouling of surfaces. In those cases titanium dioxide coating has usually been made on glass or metal surfaces (e.g. self cleaning windows). In this investigation titanium dioxide (anatase) coating was deposited on several different polyurethane surfaces to examine how it will stay on the surface and how well the titanium dioxide coating works in fouling conditions. A slurry of 2.5 % TiO2 in ethanol was prepared adjusting the pH at 1.5 with HNO3. The slurry was stirred and sonicated. After that the polyurethane plates were dipped into the slurry. The dried plates were calcined at 70 C for 2 h. After cooling the plates were washed with distilled water and dried in a heating chamber at 70 C [1]. The plates and their cross sections were characterized by SEM and FESEM to see the morphology of the surfaces. The elemental analysis was made by FESEM-EDS. The behaviour of the surfaces was investigated in outdoor conditions (1.5 months) and in laboratory conditions with methylene blue (MB). In the latter case drops of MB were pipetted on the surfaces which were irradiated with UVA radiation with the maximum wavelength of 360 380 nm. The SEM figures showed that the coating of the plates was not quite uniform but there were no differences between the plates regardless of the smoothness of the original plates. It was found that the coating did not resist mechanical scraping but was not leached away by rain. The EDS analysis confirmed that TiO2 coating remains on the surfaces and furthermore no additional inorganic compounds were found on the surfaces. In the MB experiment after nine hours irradiation the MB drop on the surface was no more visible. It was found that the coating method for the polyurethane surface should be investigated more. Because of the weak thermal stability of polyurethane it cannot be calcined at high temperatures which would make the TiO2 coating mechanically stronger. Acknowledgements This study was funded by the Finnish Funding Agency for Technology and Innovation (Tekes) from European Regional Development Fund (EAKR). References [1] S.N. Hosseini, S.M. Borghei, M. Vossouhgi and N. Taghavinia, Appl. Catal. B: Environ. 74, 53 (2007).

P35 Co-based Fischer-Tropsch Synthesis: an Operando study from catalyst activation to deactivation.
Nikolaos E. Tsakoumis1, Alexey Voronov1, Magnus Rnning1, yvind Borg2, Erling Rytter1,2 and Anders Holmen1 1 Department of Chemical Engineering, NTNU, NO-7491 Trondheim, Norway 2 Statoil R&D, Research Centre, Postuttak, NO-7005 Trondheim, Norway E-mail: tsakoumi@chemeng.ntnu.no Abstract During the last years increasing attention has been given to cobalt based Fischer-Tropsch synthesis (FTS) catalysts due to their favourable properties in terms of activity, selectivity, stability and low water-gas shift activity [1]. Despite the advantages of Co-based FTS the relatively high price of the metal requires stable operation for making process profitable. Thus, understanding the deactivation mechanisms occurring during reaction can play a key role in systems optimization [2]. Catalyst deactivation in FTS is a complex phenomenon described by two regimes of activity and selectivity variations. The first regime involves the initial stages of the reaction (days to weeks on stream) and is referred to as initial deactivation (Fig. 1), while the second regime is a deactivation with lower rate and potential irreversibility (long term deactivation). In the present work, Re promoted Co catalysts supported on -Al2O3 have been extensively studied with various techniques under in situ [3] and ex situ conditions.

Figure 1: Combined XANES/XRD in situ monitoring of FT synthesis (210oC, 18 bar & H2/CO=2.1) (a) Initial deactivation profile of Co-FTS catalyst. (b) XRD and (c) XANES graphs of the start and after ~25 h of reaction.

The employed techniques were EXAFS, XANES, XRD, Raman, and TGA-TPx. The techniques were selected in order to cover the main proposed deactivation mechanisms [2]. Monitoring the initial stages of the reaction by in situ XAS/XRD experiments at realistic FT conditions, did not show significant changes in the bulk of the crystallites e.g. sintering, carbidization, or re-oxidation (Fig. 1). The lack of bulk transformations was further confirmed by ex situ analysis and suggests that the origin of the observed deactivation is in the surface of the cobalt particles. References [1] A.Y. Khodakov, W. Chu, P. Fongarland, Chem. Rev. 107 1692 (2007). [2] N.E. Tsakoumis, M. Rnning, . Borg, E. Rytter, A. Holmen, Catal. Today, accepted. [3] M. Rnning, N.E. Tsakoumis, A. Voronov, R.E. Johnsen, P. Norby, W. van Beek, . Borg, E. Rytter, A. Holmen, Catal. Today (2009), doi:10.1016/j.cattod.2009.10.010.

P36 Photocatalytic hydrogen production from a gas phase of water and ethanol
Fabio Dionigi, Peter Vesborg, Su-il In, Ib Chorkendorff, and Sren Dahl CINF Department of Physics, Building 312, Fysikvej, DTU, Kgs Lyngby, DK E-mail: fadi@fysik.dtu.dk Abstract The search for new sustainable energy resources is attracting an increasing interest not only in the scientific community. The dream is to solve the energy and environmental issues of this century and in particular to overcome the addiction of the industrialized world on fossil fuels. A promising solution is to capture the energy of the sun and store it into the chemical bond of the hydrogen molecule by photocatalytic water splitting. The use of powdered catalyst without an applied electric bias is advantageous for its simplicity, also for the point of view of a large scale application [1]. To improve the efficiency of the catalysts is necessary to study these materials and the use of a sacrificial reagent such as methanol and ethanol is a typical test reaction because the hydrogen is produced from water more effectively [2]. As a first step in a fundamental investigation of the relation between surface structure of photocatalysts and their reactivity the activity of metal oxides and (oxy)nitrides photocatalysts have been tested in microreactors with a reactor volume of 240 nl and a gas phase obtained from an aqueous solution containing ethanol. The amount of products evolved has been measured with a quadrupole mass spectrometer. The measurable activity gives hope that activity studies can be combined with surface characterization, which will be pursued in the future.

Figure: Photocatalytic hydrogen production from a gas phase of water and ethanol using NaTaO3:La as catalyst and a mercury lamp as the light source References [1] A. Kudo and Y. Miseki, Chem. Soc. Rev., 38, 253, 2009. [2] T. Sakata, T. Kawai, Chem. Phys. Lett., 80, 341, 1981.

P37 The role of Ni and Mo species in the hydrodeoxygenation of rapeseed oil on NiMo-alumina catalysts
Peter Priecel1, Libor apek1, David Kubika2 University of Pardubice, Studentsk 573, 532 10 Pardubice, Czech Republic 2 Research Institute for Inorganic Chemistry, Zlu 1, 436 70 Litvnov, Czech Republic E-mail: peter.priecel@student.upce.cz
1

Abstract Negative prognoses for availability of fossil fuels and global warming problems place increasing emphasis upon developing and using biofuels. Hydrodeoxygenation (HDO) is a possible way to produce diesel-like fuels from vegetable oils. It offers an alternative to the transesterification producing FAME type biodiesel. Dual NiMo, CoMo or NiW supported on -alumina, primarily used as hydrodesulfurization catalysts, are typical catalysts proposed to be employed in hydrodeoxygenation.[1]. The aim of this work was to investigate the activity of NiMo-alumina catalysts in hydrodeoxygenation of rapeseed oil. The attention was focused on the study of (i) the structure analysis of active Ni species in NiMo-alumina catalysts, (ii) the comparison of the role of alumina and mesoporous alumina supports, (iii) the role of the active Ni and Mo species in the hydrodeoxygenation activity of NiMo-alumina catalysts. NiMo-alumina catalysts (2.5 wt.% Ni, 8.5 wt.% Mo) were prepared by the impregnation method. Different distribution of Ni and Mo species was achieved by varying the calcination temperature (450800 C) of the catalysts, while preserving Ni and Mo concentration. Changes in metals distribution were deduced from UV-Vis diffuse reflectance spectroscopy (DRS) and H2-TPR measurements. Crystallinity of the catalysts phases, active phase concentration and dispersion and specific surface area were investigated by XRD, XRF, SEM-EDX and N2-physisorption experiments, respectively. NiMo-alumina catalysts were tested in HDO reaction under 3.5 MPa of H2 pressure, in the 240 280 C temperature range and 1 6 h-1 WHSV range. Desired products of the reaction were C17 and C18 alkanes and oxygenated hydrocarbons were observed as intermediates. Different catalytic behaviour and reaction pathways were attributed to variation in calcination temperature of the catalysts based on the results of DRS and H2-TPR. It could be concluded that (i) the increasing pre-treatment temperature decreased the Ni(Oh):Ni(Td) (octahedral and tetrahedral nickel species) ratio affecting the activity and selectivity, (ii) the use of mesoporous alumina increased the dispersion of Mo and Ni species and also the activity of the catalysts, (iii) while Ni species supported the decarboxylation path, the Mo species supported the deoxygenation path of the reaction mechanism. Acknowledgement The authors gratefully thank to the Ministry of Industry and Trade of the Czech Republic (project FT-TA3/074) and Ministry of Education, Youth and Sports (No. MSM0021627501). References E. Furimsky, F.E. Massoth, Applied Catalysis 52, 381-495 (1999). [1]

P38 Surface and catalytic behavior of Potassium promoted Pd/Al2O3 catalysts during N2O reduction by alkanes or alkenes
G. Pekridis1, N. Kaklidis1, M. Konsolakis2,*, E. Iliopoulou3, I.V. Yentekakis2, G.E. Marnellos1,3,* 1 Department of Mechanical Engineering, University of Western Macedonia, Bakola & Sialvera, 50100, Kozani, Greece 2 Department of Sciences, Technical University of Crete, 73100 Chania, Crete, Greece. 3 Chemical Process Engineering Research Institute, Centre for Research & Technology Hellas, 6th km. Charilaou-Thermi Rd., P.O. 361, 57001 Thermi, Thessaloniki *E-mails: mkonsol@science.tuc.gr (M. Konsolakis); gmarnellos@uowm.gr (G.E. Marnellos) Abstract Nowadays, considerable attention has been dedicated on N2O abatement from flue gases, since its harmful impacts on greenhouse effect and stratospheric ozone depletion have been recently recognized [1]. To this direction, the catalytic decomposition of N2O constitutes one of the most efficient approaches. However, the inhibition induced by the strongly adsorbed oxygen species represents the main restraining factor for this direct de-N2O process. Alternatively, the catalytic reduction of N2O by hydrocarbons is a promising way to abate N2O emissions; hydrocarbons that are also present in the effluent can be used as reducing agents to facilitate the removal of oxygen ad-atoms thus eliminating O-poisoning [2]. Bearing in mind the above aspects and guided by the superior catalytic performance of Pd catalysts during N2O decomposition/reduction [2], the present study aims at exploring the effect of Potassium (K) promoter on N2O reduction by alkanes or alkenes over Pd/Al2O3 catalysts; reducing agents with different adsorption strength were employed (CH4, C3H8, C3H6) to better realize the influence of electropositive promoters on surface chemistry. It was found that Potassium strongly promotes N2O reduction by alkenes yielding 100% conversion at notably lower temperatures (ca. 100 oC) compared to those obtained over un-promoted catalysts. In contrast a slight inhibition upon K-promotion was observed when using CH4 as reducing agent, implying that the effect of Potassium promoter is strongly related with the adsorption strength of reactants/intermediates on catalyst surface. The evolution of surface behavior was identified by means of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), FTIR - pyridine adsorption (acidic properties) and TPR-TPD (metal dispersion) studies and appropriately correlated with the achieved de-N2O activity. References [1] D.J. Wuebbles, Nitrous oxide: No laughing Matter, Science 326 (2009) 56-57. [2] G. Pekridis, C. Athanasiou, M. Konsolakis, I. V. Yentekakis and G. E. Marnellos, Top. Catal. 52 (2009) 1880-1887.

P39 Structure of Ni-based catalysts active in the oxidative dehydration of ethane and propane
Lucie Smolkov1, Libor apek1, rka Botkov1, Roman Bulnek1, Frantiek Kovanda2 1 University of Pardubice, Studentsk 95, CZ-532 10 Pardubice, Czech Republic 2 Institute of Chemical Technology, Technick 5, CZ-166 28 Prague, Czech Republic E-mail: lucie.smolakova@student.upce.cz Abstract The oxidative dehydrogenation (ODH) of light hydrocarbons offers an attractive alternative to the traditional processes of ethene and propene production. However, a low ethene yield and an insufficient selectivity to ethene still prevent industrial application of ODH of ethane [1]. A large number of catalysts have been studied in the ODH of ethane and propane, i.e. mixed oxide catalysts containing, for example, vanadium, molybdenum, nickel and niobium, and supported V-, Ni-based catalysts [1]. In this work we compare the catalytic activity of (i) Ni-alumina catalysts prepared by impregnation of alumina with a solution of nickel acetate in ethanol and (ii) the catalysts prepared by thermal decomposition of Ni-Al hydrotalcite- like precursors. The attention is also given to the understanding of the active nickel species. The performance of Ni-catalysts with varying nickel loadings (0-40 wt. % Ni) and with thermal pre-treatment at 500-900 C was studied. The Ni-catalysts were characterized using X-ray diffraction (XRD) and N2-BET surface area measurements. Ni-alumina catalysts were also characterized by temperature-programmed reduction (H2TPR) and DR UV-Vis spectroscopy. The ODH of ethane was carried out in a quartz flow-through micro-reactor in the temperature range 400-600 C and atmospheric pressure. The reaction mixture consisted of 8.0 vol.% C2H6, 2.5 vol.% O2 and a rest of He was kept at a total flow of 100 ml.min-1 (W/F 0.12 gcat.s.ml-1). Ni-alumina catalysts were tested in ODH of ethane and propane at 500-600 C. There was studied the contribution of (i) tetrahedral and octahedral nickel species and (ii) Ni oxide species on the activity, selectivity, TOF and the ethene productivity [2]. Ni-Al mixed oxides were active and selective even at 400-500 C. The attention was focused to the effect of Ni/Al ratio on the activity of Ni-Al mixed oxides in ODH of ethane and propane. At 400 C these catalysts achieved comparable activity with Ni-alumina catalysts at 600 C. Acknowledgement The authors gratefully thank to the Grant Agency of Czech Republic for financial support (Projects No. P106/10/0196 and No. 203-08/H032) and Ministry of Education Youth and Sports (No. MSM0021627501) References [1] [2] F. Cavani, N. Ballarini, A. Cericola, Catal. Today 127, 113 (2007). L. apek, L. Vank, L. Smolkov, R. Bulnek, J. Adam, Collect. Czech. Chem. Commun. 73 1177 (2008).

P40 Size-selective aerobic oxidation by highly stable gold nanoparticles embedded in zeolite crystals
A.B. Laursen 1,2, K.T. Hjholt 1,3, S.B. Simonsen 1, L.F. Lundegaard 1, S. Helveg 1, S. Kegns 3, K. Egeblad 1,3, C.H. Christensen 1,3. 1 Haldor Topse A/S, Nymllevej 55, 2800 Kgs. Lyngby (Denmark) 2 DTU Chemical Engineering, DTU, 2800 Kgs. Lyngby (Denmark) 3 Center for Sustainable and Green Chemistry, DTU, 2800 Kgs. Lyngby (Denmark) Abstract In industrial heterogeneous catalysis supported metal nanoparticles are the crucial active part of the catalyst. Deactivation through sintering is one of the major deactivation routes. Hence, its prevention is the focus of several investigations, amongst others by individual particle encapsulation. From previously reported studies the encapsulation of coal nanoparticles in single crystal zeolites is well known[1]. Combining these two, we here present how to obtain a hybrid material of 1-2nm gold particles embedded in silicalite-1 zeolite crystals, as shown in figure 1[2].

Figure 1: Schematic interpretation of the hybrid metal-zeolite material and the tomography images of the produced material. The catalyst material were characterized by powder XRD, nitrogen physisorption, elemental analysis, SEM, and TEM including 3D tomography and in situ TEM imaging in oxygen atmosphere at elevated temperatures. Through this it is shown that the majority of the gold particles are encapsulated in the zeolites and that several of the nanoparticles are stable up to 550 C. This demonstrates the thermal stability of the particles; which opens the possibility of using nanoparticles of sinter prone metals in high temperature processes. Another advantage of zeolite encapsulation is the well defined access channels. The zeolite channels are of molecular dimensions; which is well known to introduce size-selective catalyst properties. The catalyst material presented here is tested for its size-selective catalytic property by the aerobic oxidation of benzaldehyde and the bulky 3,5-ditertbutylbenzaldehyde. The catalyst showed excellent properties in size-selective catalysis thus demonstrating the combined catalytic properties of this hybrid material. We believe that this will be the first of many materials that show greater sinter stability and reactant and/or product selectivity. References [1] [2] Madsen, C., Jacobsen, C.H., Chem. Commun., 673-674 (1999) Laursen, A.B. et al., Angew. Chem. Int. Ed. Accepted/in press

P41 Effective Cl-VOC removal from air on low-loaded (Au+Rh)/TiO2 catalysts

A.V. Kucherov1, S. Pitkaaho2, O.A. Kirichenko1, O.P. Tkachenko1, W. Grunert3, S. Ojala2, R.L. Keiski2 and L.M. Kustov1 1 Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia 2 Department of Process and Environmental Engineering, University of Oulu, Finland 3 Lehrstuhl Technische Chemie, Ruhr-Univeritat Bochum, Germany E-mail: akuchero2004@yahoo.com Abstract The need for efficient, HCl-resistant, and stable catalysts for Cl-VOCs removal from air is urgent, and special improvements are needed to reach the highest level of purification. In our previous study [1, 2] it was observed that the supported system (3%Rh+1%Au)/TiO2 demonstrated an impressive activity in catalytic combustion of both S-VOC and Cl-VOC. The aim of this work, based on economical aspect of the problem, is to study the system in more details and move towards a considerably lower content of noble metals supported on titania. Catalysts with 0.3-3 wt-% of Rh and 0.1-1 wt-% of Au were supported on TiO2, S 50 m2/g; by original reductive deposition method or by incipient wetness impregnation. XAS (XANES + EXAFS) study of fresh and used (3%Rh+1%Au)/TiO2 was carried out at HASYLAB (DESY in Hamburg, Germany) on the beam line X1. Catalytic removal of CH2Cl2 was studied in two modes: (1) light-off tests (~40 000 h-1 of the mixture [~500 ppm CH2Cl2 + air]); (2) at given T = 280450oC lasting 0.5-1 h. The outlet gas flow was analyzed once per min with 1 ppm sensitivity by using a FTIR gas analyzer.
1200 1000 Concentration, ppm 800
Concentration, ppm

~400 C

HCl

30

~400 C water off

600 400 200 0 110 120 130 140 Time, min 150 160 170

20

CH2Cl2

10

CH2Cl2

water off

CO
0 110 120 130 140 Time, min 150 160 170

(water effect)

Fig. 1. Catalytic oxidation of 520 ppm of CH2Cl2 at 400oC on (0.1%Au+0.3%Rh)/TiO2.

Low-loaded catalysts provide stable and effective CH2Cl2 oxidation at T ~ 400oC (Fig. 1). No extrawater supply is needed for effective HCl formation. Catalysts are stable upon high-temperature treatment. References [1] A.V. Kucherov, S. Pitkaaho, I.M. Sinev, O.A. Kirichenko, S. Ojala, R. Keiski and L.M. Kustov, EuropaCat-9, 30 Aug.4 Sept. 2009, Salamanka, Spain, Abstracts, p. 350. [2] A.V. Kucherov, O.P. Tkachenko, O.A. Kirichenko, G.I. Kapustin, I.V. Mishin, K.V. Klementiev, S. Ojala, L.M. Kustov, and R. Keiski, Top. Catal., 52, 351 (2009).

P42 Peculiarities of VOC, S-VOC, and Cl-VOC removal from exhaust gases over oxidation catalysts of different types
A.V. Kucherov1, S. Pitkaaho2, O.A. Kirichenko1, S. Ojala2, A.L. Kustov1, E.Z. Golosman3, L.M. Kustov1 and R.L. Keiski2 1 Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia 2 Department of Process and Environmental Engineering, University of Oulu, Finland 3 Institute of Nitrogen Industry, Novomoskovsk, Tulskaya obl., Russia E-mail: akuchero2004@yahoo.com Abstract In spite of a considerable progress reached during the last years in catalytic purification of exhaust gases from volatile organic compounds (VOC), the problem becomes more complicated in the case of removal of toxic and malodorous sulfur-VOCs and chlorine-VOCs. Stable and reasonably cheap catalysts must provide much deeper purification levels without formation of such products as SO3 and Cl2. In our study [1-3] we tested a variety of mono- and bi-metallic catalysts containing noble metals (such as Rh, Pd, and Au), as well as mixed oxide catalysts. The aim of our work was to compare peculiarities of oxidation of all three forms of organics (VOC, S-VOC and Cl-VOC) on catalysts of different types. Supported (Au+Rh)/TiO2 catalysts (including low-loaded samples) demonstrate an impressive efficiency in exhaust gas purification from both Cl-VOCs and S-VOC at T 330C and high space velocities. Catalysts are SO2- and HCl-resistant and stable upon high-temperature treatment. No extrawater supply is needed for effective HCl formation upon Cl-VOC oxidation. Inexpensive mixed oxide CuO-MnO2-binder (the Hopkins-type catalyst) demonstrates an effective oxidation of VOC. On the other hand, application of this industrial-type catalyst for deep purification of air pollutants, i.e. S-VOC and Cl-VOC is restricted. The starting content of SO2 or HCl in the outgoing flow is low due to effective absorption (chemical bonding) of these compounds by the catalyst bed. The catalyst is gradually irreversibly modified by sulfite/sulfates (or chloride) formed upon S-VOC (Cl-VOC) removal. The poisoning effect is very pronounced in the case of Cl-VOC oxidation and results in drastic activity loss. The life time of the efficient work of the catalyst seems to be longer in the case of S-VOC removal. Supported perovskite, LaCoO3/ZrO2, shows a reasonably high efficiency in the oxidation of all the three organic compounds. In the case of Cl-VOC no irreversible loss of activity occurs upon a long-term testing. Extra-water supply promotes a more effective HCl formation. However, this catalyst provides a lower purification level, as compared with (Au+Rh)/TiO2. References [1] A.V. Kucherov, I.M. Sinev, K.I. Slovetskaya, S. Ojala, R. Keiski, E.Z. Golosman, and L.M. Kustov, NORDIC-13, 5-7 Oct. 2008, Goteborg, Sweden, Abstracts, p.105. [2] A.V. Kucherov, O.P. Tkachenko, O.A. Kirichenko, G.I. Kapustin, I.V. Mishin, S. Ojala, L.M. Kustov, and R. Keiski, 14 Intern. Congr. on Catalysis, July 13-18, 2008, Seoul, Korea, Abstracts, p.328. [3] A.V. Kucherov, I.M. Sinev, S. Ojala, R. Keiski and L.M. Kustov, Studies Surf. Sci. Catal. 170, 1129 (2007).

P43 Origin of in-situ reduction and oxidation of Co/Al2O3 in the Fischer-Tropsch Synthesis
Jia Yang, Tiejun Zhao, Erik Tveten, De Chen, Anders Holmen Department of Chemical Engineering, Norwegian University of Science & Technology NO-7491 Trondheim Norway E-mail: Jia.Yang@chemeng.ntnu.no Co/Al2O3 catalyst presents a high activity and high C5+ selectivity in Fischer-Tropsch Synthesis (FTS). The evolution of the cobalt species such as oxidation and reduction behaviour in reaction conditions of FTS is considered as one of key issues responsible for the stability of the catalyst.[1] However, the mechanism of the in-situ reduction and oxidation of Co catalyst remains unclear. In this contribution, we couple the isotopic labeling and temperature programmed hydrogenation (TPH) method to study the insitu reduction and oxidation of Co catalyst, thus giving the mechanistic information for the transformation pathway of Co species during the interaction with the syngas. Typically, the fresh reduced 20% Co/Al2O3 catalyst was exposed to C18O at 210C and then flushed with Ar, followed by isothermal hydrogenation at 210C and TPH experiment by flowing the pure hydrogen (15 ml/min) with a temperature ramp (10 K/min) from 210 to700C. Another comparative experiment is carried out by flushing the syngas prior to the isothermal hydrogenation experiment. The outlet gases such as CH4 and H2O are monitored by a mass spectroscopy, to gain the information of bonded C* and O* species on the Cobalt surface. The appearance of H218O spectra in mass spectroscopy is proposed due to the reduction of Co18O, which is in-situ produced via the oxidation of metallic Co by C18O. The consistence between H2O (originated from the unreduced CoO) and H218O spectra confirmed the formation of Co18O. It was found out that the amount of strongly bonded O* and 18O* surface species was significantly deceased through the syngas treatment, whereas the amount of strongly bonded C* surface species was not changed. This means that not only can syngas further reduce the residual cobalt oxides (mostly, CoO) in the fresh reduced Co catalyst (in-situ reduction), but also limit the in-situ oxidation of the metallic cobalt. This observation also indicated that the syngas had stronger reduction ability than H2 alone. Earlier appearance of CH4 peak than H2O as indicated by the corresponding spectra in the isothermal hydrogenation experiment suggested that the hydrogenation rate of surface C* was much faster than surface O* at 210C. The rate of oxygen removal increases with the following order: O*+H2 < O*+CO <O*+CO+H2, suggesting that syngas or more specifically reaction intermediates (CHxOy*) was more effective for removing surface oxygen compared to pure H2 and CO. In-situ oxidation of cobalt and in-situ reduction of cobalt oxide took place simultaneously under the FTS condition, and the overall effect depends on the extend of individual reduction and oxidation, which is determined by the Co particle size, H2/CO ratio, temperature etc. References [1] A.M. Saib, A. Borgna, J. van de Loosdrecht, P.J. van Berge and J.W. Niemantsverdriet, Appl. Catal. A 312, 12 (2006).

P44 The SET Model for Catalysis

Ragnar Larsson Chemical Engineering II, Chemical Center, University of Lund, Lund, Sweden E-mail: ragnar-larsson@telia.com Abstract Some years ago a model for the activation of a catalytic process was proposed [1]. The main idea of this model was that the energy necessary for the activation process was transferred via a resonance process from a vibration mode of the catalyst system to a vibration mode of the molecule that was to react. This latter vibration should be such that the reaction was made possible. Obviously the resonance condition demands that the wave number of the catalyst vibrator () and the wave number of the critical vibration mode of the reactant () should be as near to each other as possible. The condition for this Selective Energy Transfer (SET) was defined [1] and it was shown that, inter alia, the so called Isokinetic Temperature for a series of almost equal ( but not identical) catalysts could be expressed in terms of the above-mentioned wave numbers. Since then a number of catalytic systems has been investigated [ 2- 5]. It has been found that the isokinetic temperature can be calculated with a good to excellent accuracy, once the critical vibration had been identified. In some cases a resonance occurs so that, e.g., four quanta of interact with five quanta of . This is exemplied in [3 ] where the Ni-H vibration at 940 cm-1 interacts with o.o.p C-H bending vibration at 740 cm-1.Incidentally, we found Tiso = 669 2 K and calculated from the frequencies given Tiso = 669 K. It has also been found [2,4] that the experimentally determined activation energies can be expressed in terms of the wave numbers . From an analysis of the activation energies one can determine the vibration frequency and also the anharmonicity of the vibration. References [1] R. Larsson, J .Mol. Catal. 55, 70 (1989) [2] R. Larsson, M H Jamroz and M.A. Borowiak, J. Mol. Catal .A 129, 41 (1998). [3] M.A. Keane and R. Larsson, J. Mol. Catal .A 268, 87 (2007). [4] M.A. Keane and R. Larsson, Catalysis Communications 9, 333 (2008). [5] K.M. Bratlie, Y. Li, R. Larsson and G.A. Somorjai, Catal. Lett. 121, 173 (2008).

P45 Selective Growth of SWNTs from CuOx-FeOx Catalyst

Maoshuai He1, Emma Rikkinen1, Kati Vilonen , ElenaObraztsova2, Zhen Zhu2, Hua Jiang2, Esko I. Kauppinen2, Marita Veringa Niemel1, A. Outi I. Krause1 1 Department of Biotechnology and Chemical Technology, Aalto University, Finland 2 NanoMaterials Group, Aalto University, Finland 3 A.M. Prokhorov General Physics Institute RAS, Moscow, Russia E-mail: maoshuai.he@hut.fi Abstract Single-walled Carbon Nanotubes (SWNTs) are regarded as potential building blocks in nanoelectronics. Obtaining SWNTs with narrow (n,m) chirality distribution are highly desirable since the electronic properties of SWNTs strongly depend on their diameter and chirality. Herein, we report the growth of small diameter SWNTs from CuOx-FeOx catalysts deposited on MgO. Various techniques were employed to analyze both the catalysts and SWNTs: Temperature Programmed Reduction (TPR), Raman, Absorption and Fluorescence Spectroscopy, ultra-high resolution transmission electron microscope (Jeol JEM-2200FS double Cs corrector TEM). TEM has convinced that nanoparticles with diameters 2 to 4 nm were deposited onto MgO. It was shown in Fig. a that small diameter SWNTs with high quality have grown successfully from the catalyst even at 600 C. SWNTs diameters mainly range from 0.7 nm to 0.9 nm. UV-vis-NIR spectra of SWNTs produced at different temperatures are shown in Fig. b. Decreasing the reaction temperature leads to a progressive narrowing of the diameter distribution, this result is coincided with Raman spectra, photoluminescence intensity maps. Meanwhile, the mechanism for successful growth of SWNTs by CuFe contained catalyst has been discussed.
1

Figure (a). Raman spectra of SWNTs grown at different temperatures (inset is a TEM image of nanoparticles); (b) UV-Vis-NIR absorption spectra of SWNTs grown at different temperatures. References S. M. Bachilo, L. balzano, et al. J. Am. Chem. Soc, 125, 11186 (2003). [1] [2] S. Lim, C. Wang, et al. Catal. Today. 123, 122 (2007).

P46 Selective catalytic reduction of NO with ethanol over carbon nanotube supported catalysts
Mari Pietikinen1, Anna Avila1, Mika Huuhtanen1, Tanja Kolli1, Krisztian Kords2, Riitta L. Keiski1 1 Dept. of Process and Environmental Eng., POB 4300, FI-90014 University of Oulu, Finland 2 Dept. of Electrical and Information Eng., POB 4500, FI-90014 University of Oulu, Finland E-mail: mari.pietikainen@oulu.fi Abstract The catalytic activity of novel carbon nanotube (CNT) supported Pt, Pd and Rh nanoparticles in selective catalytic reduction (SCR) of NO using ethanol as a reductant is studied. Due to the growing demand for biobased energy sources, the use of ethanol as a fuel will increase [1]. Ethanol is a non-toxic and safe chemical, thus ethanol is an excellent choice to be used as a reductant in the SCR process of passenger cars. Platinum group metals (PGM) are reported to have good ability to catalyse NO reduction by hydrocarbons at low temperatures and in lean-burn conditions [2]. The catalysts were prepared by wet impregnation. The structure and composition of the synthesized catalysts were analysed by TEM, SEM-EDX and XRD methods. Based on the analyses the Pt, Pd and Rh metal loadings on the CNT catalysts were 6.21.2 wt-%, 5.31.5 wt-% and 2.80.3 wt-%, respectively. The activity of the catalysts (packed in quartz wool) was tested in a laboratory scale quartz tube reactor (space velocity of ~24 000 1/h) using a reaction gas mixture of 1000 ppm NO, 2000 ppm C2H5OH, 10 vol-% O2 and 10 vol-% H2O balanced with nitrogen. During the experiment the temperature of the reactor was risen from 100 C to 300 C with a heating rate of 5 C/min. C2H5OH and H2O were fed to the reactor as liquids using a peristaltic pump. The outlet gas composition was measured by a FTIR gas analyser. Preliminary results show very efficient low temperature reduction of NO with ethanol with maximum NO conversions of >99%, >98% and ~85% for the Pt, Pd and Rh/CNT catalysts, respectively. The optimum operation temperatures for CNT catalysts were found to be as low as 210250 C for the Pt and Pd/CNT catalysts and 280300 C for the Rh/CNT catalyst. Considerable formation of undesired N2O was not observed in the experiments. In conclusion, Pt, Pd and Rh/CNT catalysts are promising materials for the low temperature ethanol assisted SCR of NO. References [1] European Parliament and Council (2009). Directive 2009/28/EC. [2] R. Burch et al., Appl. Catal. B: Environ. 39, 283 (2002).

P47 Novel CNT-based catalyst materials for low temperature NH3-SCR of NO

Anna Avila1, Anne-Riikka Leino2, Mika Huuhtanen1, Tanja Kolli1, Krisztin Kords2, Riitta L. Keiski1 1 Dept. of Process and Environmental Eng., POB 4300, FI-90014 University of Oulu, Finland 2 Dept. of Electrical and Information Eng., POB 4500, FI-90014 University of Oulu, Finland E-mail: anna.avila@oulu.fi Abstract Selective catalytic reduction of NOx by ammonia (NH3-SCR) is a well-proven technique for NOx abatement. The growing concern about the environment has, however, increased the need of development of more efficient catalysts for emission control [1]. Low temperature NH3-SCR could be one solution to fulfil the requirements. Recently, carbon nanotubes (CNTs) are considered as interesting support materials for future catalyst applications because of their unique structure and properties [2]. Noble metals are used in NH3-SCR at low temperatures [3]. The aim of this study was to prepare Pt/CNT and Pd/CNT catalysts and investigate the suitability of the prepared catalysts for NH3-SCR of NO at low temperatures. Carboxyl functionalized multi-walled CNTs were used to prepare CNT-based Pd and Pt catalysts by a wet impregnation method. The structure and composition of the synthesized catalysts were analysed by TEM, SEM, EDX and XRD methods. Activity and selectivity of the prepared catalysts and carboxyl functionalized CNTs (CNT-COOH) were investigated in the NH3-SCR model reaction in a laboratory scale quartz tube flow reactor at atmospheric pressure. The product gas was analysed by a FTIR gas analyser. Used reaction conditions were 1000 ppm NO, 1000 ppm NH3, 10 vol-% O2 and N2 as balancing gas. The flow rate was 1000 ml/min corresponding to GHSV of 24 000 h-1 and temperature was increased from room temperature to 300C at a heating rate of 5C/min. According to the characterisation results of the prepared catalysts it was found out that Pt and Pd were deposited as well dispersed nanosized particles on the CNTs. The metal loadings of Pt/CNT and Pd/CNT were 6.21.2 wt-% and 5.31.5 wt-%, respectively. Average particle sizes measured by TEM were found to be below 4 nm for each catalyst. According to XRD, Pd is in metallic/oxide form (Pd/PdO) and Pt is detected as metallic in Pt/CNT. The results of the activity measurements show that prepared catalysts are active in NH3-SCR at temperatures below 300C. The maximum NO conversions over Pt/CNT and Pd/CNT were 86% and 55%, respectively, whereas the parent CNT-COOH was not active during the experiment. However, the selectivity towards N2 of the prepared catalysts was not as high as expected. Especially over Pt/CNT undesired formation of by-products such as N2O, NO, CO2 and CO was high. The NH3 conversion was >90% in both cases. The prepared CNT catalysts are found to be promising materials in NH3-SCR of NO with a dry gas mixture. Further studies will be carried out to investigate the suitability of the prepared catalysts for NH3-SCR of NO in moist conditions. References [1] European Parliament and Council (2007). Regulation (EC) 715/2007. [2] P. Serp, M. Corrias and P. Kalck, Appl. Catal. A Gen. 253, 337 (2003). [3] M. Radojevic, Env. Poll. 102, 685 (1998).

P48 The study of modified activated carbon characteristics by adsorption methods

Hoang Kim Bong, Oleg N. Temkin, Hoang Huu Binh, N.T. Kartel* and D. I. yamandy. Moscow State Academy of Fine Chemical Technology named after M.V. Lomonosov. Tel: (07)(495)936-8904; Fax:(07)(495)434-8711. E-mail:hoang46@mail.ru *O.O. Chuiko Institute of Surface Chemistry, NAS of Ukraine Tel:+380444238058, E-mail: nikar@kartel.kiev.ua It has been shown [1-3] that the oxidation of activated carbons (AC) by nitric acid highly influences their adsorption capacity as to benzene, acetic acid and salt catalysts. The Zn(OAc)2/C supported AC catalysts exceed in activity the Montecatini MAVC catalyst [3], one of the best in vinylacetate synthesis. The investigations of other ways of AC surface modification (AC treatment by acetic acid and H2O2) have demonstrated that obtained AC to have boath an increased adsorption capacity as to Zn(OAc)2, optimum volumes of meso- and micropores and high catalyst activity in vinyl acetate (VA) synthesis[2]. The results of these investigations are given below. The characteristics of supports were found out by benzene, ethanol, water and acetic acid vapours adsorption by means of vacuum adsorption laboratory installation with McBen scales, under initial pressures of 10-4 10-6 torr at temperature 25 oC. Modified sorbents characteristic properties. The AGN-2 AC porous structure after H2O2 treatment (AGN-2K) changed greater than after AcOH (AGN-2U) treatment. The mesopores volume increased by approx. 25%, the specific surface area value of AGN-2K increased by 40 m2/g reaching 91010 m2/g. By AC oxidation the partial decarboxylation takes place. Judging by the results of elemental analysis on C and H of oxidized carbons (AGN-2) by H2O2, H/C ratio after carbons treatment with H2O2 increases from 0,35 to 0,52, the adsorption capacity as to water, ethanol and benzene increasing as well. On the oxidized AC the number of available adsorption sites on both polar (H2O, CH3COOH) and non-polar (benzene) compounds as well as the adsorption capacity (a) increased by 25-30%. However, at full surface pores filling (P/Ps=0,8) the (a) value of benzene increased by 14%, and that of water by 36%, the heat of water adsorption H2O increased by 58 kJ/mole, and that of benzene approx. by 7 kJ/mole (Tabl.): Table Dependence of adsorption heat on methods and treatment of activated carbon C6H6 H2O -1 Sample AC (kJmole ) (kJmole-1) AGN-2 53,5 40,1 AGN-2 60,6 98,2 Adsorption capacity (on oxidized surface AGN-2 with H2O2) as to AcOH rises sharply as is shown on. The relatively higher growth of surface polarity (hydrophilicity) is also confirmed by adsorption capacity increase as to methylene blue (2,5 times approx.). These changes of surface properties (together with mesopores volume increase) became apparent in growing of adsorption capacity as to zinc acetate [3]. AC, treated by AcOH, changed its porous structure slightly as shown by adsorption measurement results (fig.3), though that part of supermicropores with radius of approx. 5 (as of according) to SAXS measurements increased by approx. 40%. The minor expanding of mesopores caused by removal of

impurities and small quantity of resins left after activation can be observed (the third peak on fig.3) as well. References 1). Hoang Kim Bong, O.N. Temkin //17th North American Catalysis Society Meeting, Toronto, Ontario, Canada, June 3-8, 2001. 2). Hoang Kim Bong, Temkin O.N.// Thesis at International symposium Carbon for catalysis (Carbocat-2004, July 18-20, 2004) Lausanne, Switzerland. 3). Hoang Kim Bong, Kurlyandskaya I.I, Temkin O.N., Hoang Huu Binh and Zanaveskin K. L. This Conference (2006).

P49 Influence of thermal pretreatment on the catalytic performance of Pd-Sb/TiO2 catalysts for acetoxylation of toluene
N. Madaan, S. Gatla, V.N. Kalevaru, J. Radnik, B. Lcke, A. Brckner, A. Martin Leibniz Institute for Catalysis at University of Rostock, Rostock, Germany E-mail: neetika.madaan@catalysis.de, Tel. +49-381-1281-296, Fax. +49-381-1281-51296 Direct and controlled partial oxidation of various hydrocarbons to get desired oxygenates is one of the greatest demands in heterogeneous catalysis. Acetoxylation of toluene to benzyl acetate via gas phase oxidation is one such example. Benzyl acetate (BA) is a fruity smell ester, which is extensively used in perfumery, food and chemical industries. Traditionally, Pd based catalysts are widely used for acetoxylation reactions. From earlier studies, PdSb system was found to be highly active and selective among various catalysts investigated. However, low initial activity, longer induction periods and subsequent deactivation after 10 hours-on-stream are some of the problems of this catalyst system [1], which need to be solved yet. Based on this observation, the main objective of this study is to develop highly active and selective catalysts with longer life time and to reduce such induction period (10 h). For this purpose, we have prepared Pd-Sb/TiO2 catalyst with various modifications such as changed source of Pd precursor, altered preparation method and varying thermal treatments. The intention is to investigate the catalytic performance of these solids for acetoxylation of toluene to check the effect of thermal treatment. 10%Pd-16%Sb/TiO2 (anatase) was prepared by a two-step impregnation procedure involving i) impregnation of anatase with Sb2O3 precursor (instead of earlier SbCl3) followed by ii) impregnation with PdCl2.. The prepared catalyst was subjected to three different thermal treatments prior to testing such as i) direct activation in the reactor at 300 C/2 h/air, ii) external calcination at 400 C/4 h/He), and iii) calcination at 600 C/4 h/He. Catalytic tests were performed in a fixed bed stainless steel reactor at 210 C and 2 bar. Product stream was analysed every hour with off-line GC. Further, catalysts were characterised by XRD, ICP-OES. Catalytic results obtained from these samples differed considerably, indicating a clear influence of thermal treatment on the performance. For instance, the catalyst activated directly in reactor gave X-Tol = 65 % & S-BA = 85 %. This trend is more or less similar to the one observed earlier [1]. In addition, low initial activity and fast deactivation (after 10 hours) was observed. XRD showed the formation of Na2PdCl4 phase in this fresh catalyst, which is however vanished completely in spent sample and only metallic Pd phase was observed. To get this active metallic Pd phase in the fresh catalyst itself, solids were thermally treated at higher temperature (400 C and 600 C) in helium. However, XRD pattern of this fresh solid showed both metallic Pd and Na2PdCl4 phases. The solid treated at 400 C/He showed somewhat increased lifetime and stability. Nevertheless, lower initial activity was still present. On the other hand, XRD of fresh solid treated with 600 C/4 h/He has shown slight shift in the metallic Pd peaks compared to previous two samples. Interestingly, this sample displayed much superior performance X-Tol = 51 % & S-BA = 91 % with significant decrease in induction period from 10th hour to 5th hour and good long-term stability over 30 hours of operation compared to only 10 hours on the earlier sample. Thermal treatment has shown a clear influence on the behaviour of the catalysts. Good long-term stability with reduction of initial formation period was successfully achieved for 10Pd-16Sb/TiO2 600 C/ 4 h/He catalyst. [1] K. V. Narayana, A. Benhmid, J. Radnik, B. Lcke, A. Martin, J. Catal. 243 (2006) 25

P50 Monsanto carbonylation by Supported Ionic Liquid Phase (SILP) catalysis

Christopher W. Hanning, Rasmus Fehrmann, Anders Riisager, Olivier Nguyen Van Buu Centre for Catalysis and Sustainable Chemistry, DTU Chemistry, 2800 Lyngby, Denmark E-mail: chhan@kemi.dtu.dk Abstract The boom in ionic liquid research in the last decade has led to their usage as reaction media in a vast array of catalysed reactions and separation systems. Despite this the overarching problem of ionic liquids remains their high costs compared to more traditional organic solvents. This is an important issue on industrial scales when a direct switch of solvent to ionic liquid would result in significant increases in capital costs. The concept of Supported Ionic Liquid Phase (SILP), removes this issue of high volumes by making use of the typical heterogeneous catalysis concept of using a support material to contain the ionic liquid phase, significantly reducing the required liquid volumes [1].

Figure 1 : Schematic illustration of the SILP concept. We have demonstrated the SILP concept to the carbonylation of methanol for the production of the commodity chemical acetic acid [2]. The work is based on the traditional rhodium Monsanto system, used industrially for acetic acid synthesis, but by the application of SILP catalysis. This allows the current homogeneous batch process to be switched to a continuous fixed-bed process with the use of a heterogeneous like catalyst. The present work has focused on elucidating effects induced by use of both various rhodium precursors and ionic liquids for the carbonylation reaction. The results obtained so far, seem to indicate that the traditional reaction scheme is not sufficient to describe the product distribution for the SILP gas-phase reaction. As previously reported [2], the variation of reaction conditions, especially in such a gas phase reaction, can dramatically the alter product distribution seen when compared to the industrial batch processes. Overall the work has confirmed SILP carbonylation as a viable synthetic route to acetyls. References [1] A. Riisager, R. Fehrmann, M. Haumann, P. Wasserscheid, Eur. J. Inorg. Chem. 2006, 695. [2] A. Riisager, B. Jrgensen, P. Wasserscheid, R. Fehrmann, Chem. Commun. 2006, 994.

P51 Rhodium-based catalysts promoted by Lithium on Si/Zr mesoporous oxides applied in syngas to ethanol conversion
Luis Lpeza,b,*, Robert Anderssona, Jorge Velascoa,b, Sal Cabrerab, Magali Boutonneta, Sven Jrsa, a Royal Institute Of Technology KTH, Stockholm - Sweden. b Instituto de Investigaciones Qumicas UMSA, La Paz - Bolivia. * E-mail: lgln@kth.se

Today ethanol in fuel-grade accounts for roughly two-thirds of world ethanol production [1]. Catalytic process for the conversion of syngas (CO+H2) to ethanol is a promising way to produce ethanol. Among the catalysts reported in the literature, rhodium-based have showed selectivity to C2-oxygenates compounds, in which the incorporation of metal promoters such as alkali (lithium, potassium, etc.) and transition (Zirconium, Manganese, etc.) reduces the methane formation. Mesoporous silica (MCM-41) as support is highly selected in heterogeneous catalytic applications due its high surface area. In this work we have synthesized mixed mesoporous oxides of Silicon and Zirconium (molar ratio Si/Zr=129, 30, 19) by sol-gel method (atrane route, [2]), in which 0.4% Lithium and 1.6% Rhodium were added using the wetness impregnation method. Catalytic tests were performed in a stainless-steel fixed-bed reactor at pressures of 10 and 50 bar and temperatures of 257, 300 and 357C. A syngas with a 2H2/CO molar ratio was used as feed. Ethanol and other reactions products were analyzed by gas chromatography. The catalysts have a porosity in the range of mesoporous as showed by XRD (peak near to 25*2 at low angle mode) and BET (26-29 pore size by BJH) analysis. The surface area of the catalyst decreases compare to SiO2-pure (1256 m2/g) as shown in Table 1. Incorporation of an increasing amount of Zirconium reduces the surface area of the catalyst. Even though, surface areas are higher, approx. 800 and 50m2/g, compared to commercial Silica and Zirconia respectively.
Table 1. Catalytic test for ethanol production from syngas on catalysts synthesized by atrane route. Catalyst Pressure Temperature Conversion EtOH MetOH CH4 Surface (bar) of CO (%) (%) (%) (%) area (C) (m2/g) 50 257 0.20 7.03 48.00 37.45 855 30Si/Zr-Rh-Li 50 300 2.44 10.59 27.31 50.19 855 50 357 19.41 6.39 6.70 77.37 855 19Si/Zr-Rh-Li 50 300 4.33 5.10 16.72 69.18 712 129Si/Zr-Rh-Li 50 300 4.61 5.04 22.74 69.06 986

TPR profiles show two peaks around 125 and 400C that correspond to the reduction of the Rhodium oxides to metallic Rhodium. The catalysts were pretreated in hydrogen before the catalytic tests. The results of the syngas conversion are shown in Table 1. At 50 bar, the highest selectivity toward ethanol was obtained with the 30Si/Zr-Rh-Li catalyst, while lower selectivities were found for 19/Zr-Rh-Li and 129/Zr-Rh-Li catalysts with high and low Zirconia content, respectively. The CO conversion on 30Si/Zr-Rh-Li catalyst increases with the temperature. At the same time, methane production of increases while the methanol production decreases. References [1] Saxena, R., D. Adhikari, and H. Goyal, Renewable and Sustainable Energy Reviews 2009. 13: p. 167-178 [2] Cabrera, S.; El Haskouri et al. J. Soil Sci. 2, 405420, 2000

P52 Density functional study on ethylene decomposition on flat and stepped Palladium
1

J. Andersin1 , K. Honkala1,2 Department of Chemistry, P.O. Box 35, University of Jyvskyl, 40014 Jyvskyl, Finland 2 Department of Physics, P.O. Box 35, University of Jyvskyl, 40014 Jyvskyl, Finland E-mail: karoliina.honkala@jyu.fi

Abstract Ethylene (CH2CH2) adsorption and decomposition to atomic carbon and hydrogen over Pd(111) and Pd(211) surfaces have been studied with the aim to unravel the complex chemistry of this industrially relevant reaction [1,2]. We have constructed a potential energy surface containing information of the energetics of ethylene decomposition pathway (see Figure 1). In unison with the experiments our calculations show that ethylidyne (CCH3) is the most stable molecule among the ethylene decomposition residues. Our results also support the experimental findings indicating that decompositions come into action in a progressive order with increasing temperature: Calculated activation barriers related to ethylidyne decomposition to atomic carbon are around 0.5 eV higher compared to ethylene-ethylidyne conversion on flat Pd. Step edges scramble the picture by offering active sites for adsorbates and facilitating certain reaction mechanisms. The reaction and activation energies for processes involving the activation of C-H bond are directly proportional, and the linear response is outstanding for the flat surface.

Figure 1: Potential energy diagram for ethylene decomposition on Pd(111) and Pd(211) surfaces. Black (green) line represents the adsorption energies of the different hydrocarbon species on Pd(111) (Pd(211)). Transition state energies are illustrated with curved lines. The zero of energy is ethylene far away from the clean surface.

References [1] J. Andersin and N. Lopez and K. Honkala, J. Phys. Chem. C 113 (2009) 8278 [2] J. Andersin and K. Honkala, Surf. Sci., in press

P53 Ce-Zr based catalysts in CWAO process

1

Rahikka, L.1,2, Heponiemi, A.1, Lassi, U.1,2 University of Oulu, Department of Chemistry, P.O.Box 3000, FIN-90014 University of Oulu 2 Kokkola University Consortium Chydenius, P.O.Box 569, FIN 67101 Kokkola E-mail: laura.rahikka@oulu.fi

Abstract Catalytic wet air oxidation (CWAO) can be used to remove organic pollutants from industrial wastewaters [1]. Several noble metal catalysts, such as Ru, Pt, Rh, Ir and Pd, can be used in these reactions [2]. Recently, zirconia supported ruthenium catalysts have been widely studied because of their chemical resistance in CWAO processes [3]. In this study, supported iridium and ruthenium catalysts (Ir/Ce0.85Zr0.15O2, Ir/Ce0.2Zr0.8O2, Ru/Ce0.85Zr0.15O2, and Ru/Ce0.2Zr0.8O2) were used in the oxidation of dilute ethanol solutions. Ru and Ir concentrations in the catalysts were 0.5 w-% and 2.6 w-%, respectively. Industrial ethanol containing wastewater solution was used as a reference sample. The aim was to study the effects of the preparation methods of these catalysts on the oxidation activity of ethanol. Ce-Zr based mixed oxide supports were prepared by sol-gel method. Catalytic active metals were added by wet impregnation and catalysts activated under hydrogen gas flow at 350C or 650C. Oxidations of ethanol model solutions (25 mL L-1) and industrial reference sample (68 mL L-1) were carried out in a stainless steel autoclave using air as an oxidizer. Catalyst load was 4 g L-1. Water samples were analyzed by GC, TOC and COD. Gas samples were analyzed on-site by FTIR. Fresh and used catalysts were characterized by TEM, XRD and BET. According to the results, Ru/Ce0.85Zr0.15O2 catalysts activated at 650 C seems to have higher activities in oxidation reactions than Ru/Ce0.2Zr0.8O2. Ru/Ce0.85Zr0.15O2 catalysts have also higher surface areas. The average metal particle size was 1-3 nm for the fresh Ru/Ce0.85Zr0.15O2 and Ru/Ce0.2Zr0.8O2 catalysts and 1.5-3.3 nm for the used catalysts. Significant differences in oxidation activities between Ir and Ru catalysts were not observed. Ir catalysts were active also when lower activation temperatures were used. References [1] [2] [3] Debellefontaine, H.; Chakchouk, M.; Foussard, J.N.; Tissot, D.; Striolo, P. Environ. Pollut. 92, 155-164 (1996). Pirkanniemi, K, Sillanp M. Chemosphere 48, 1047-1060 (2002) Pintar, A.; Batista, J.; Tisler, T. Appl. Catal. B 84, 30-41 (2008)

P54 Catalytic wet air oxidation and photocatalysis in the removal of ethanol from wastewaters
Rahikka, L.1,3, Lenkkeri, R.2, Piril, M.2, Heponiemi, A.1, Lassi, U.1,3, Kuokkanen, T.1, Keiski, R.L.2 1 University of Oulu, Department of Chemistry, P.O.Box 3000, FIN-90014 University of Oulu 2 Univ. of Oulu, Dep. of Process and Env. Eng., P.O.Box 4300, FIN-90014 University of Oulu 3 Kokkola University Consortium Chydenius, P.O.Box 569, FIN 67101 Kokkola E-mail: laura.rahikka@oulu.fi Abstract Photocatalysis and catalytic wet air oxidation (CWAO) can be used to remove organic pollutants from industrial wastewaters. From these two methods the photocatalytic method is convenient for dilute wastewater solutions. The two methods were studied and compared in the removal of 2.5-25 mL L-1 ethanol from aqueous solutions. In CWAO ceria-zirconia based ruthenium catalysts were used to improve the efficiency of oxidation reactions. CWAO experiments were carried out in a stainless steel batch reactor using air as an oxidizer. The volume of the sample was 270 mL (concentration of ethanol 25 mL L-1) and the reaction conditions were: temperature 150C and pressure of the air 3.5 bar. Catalyst load was 4 g L-1. Samples were taken periodically from the reactor during the experiments. The reduction of ethanol was measured by GC and organic concentrations of the water samples were analyzed by TOC (Total Organic Carbon) and by COD (Chemical Oxygen Demand). Ethanol solution was oxidized in the presence and absence of a catalyst. After 30 minutes 87% reduction of ethanol was achieved in non-catalytic reactions and 96% reduction in the catalytic ones. TOC reduction was 89% (non-catalytic) and 97% (catalytic) after 30 minutes reaction. Compared to the photocatalytic reactions CWAO seems to be a more efficient treatment method in the removal of ethanol from water solutions. The photocatalytic experiments were carried out in an annular type batch reactor at room temperature using air as the oxidizer. One liter of reaction slurry having 2.5 mL ethanol and 1 g titanium dioxide catalyst (Degussa P25) was irradiated at 52 W m-2 by an UV lamp placed in the middle of the reactor and having the maximum radiation at the wavelength of 350360 nm. Before switching on the lamp there was a 30 min dark period to stabilize the reaction conditions. The reduction of the ethanol in the reaction was measured by GC. The TOC and COD of the solution were also measured. After five hours experiment the conversion of the ethanol was 29%, TOC reduction 12% and COD reduction 16% indicating that complete mineralization had not taken place during the measurement time. It was found that the reduction of ethanol without the catalyst was negligible. Acknowledgements This study was funded by the Finnish Funding Agency for Technology and Innovation (Tekes) from European Regional Development Fund (EAKR) and Maj and Tor Nessling Foundation.

P55 Effect of Pt nanoparticle size in the deep oxidation of C1-C6 n-alkane

A.M. Gololobov1, I.E. Bekk2, G.O. Bragina1, V.I. Zaikovskii2, A.B. Ayupov2, N.S. Telegina1, V.I. Bukhtiyarov2, A.Yu. Stakheev1 1 Zelinsky Institute of Organic Chemistry RAS, 119991, Leninsky Prosp. 47, Moscow, Russia 2 Boreskov Institute of Catalysis SB RAS, 630090, Prosp. Lavrentieva 5, Novosibirsk, Russia E-mail: st@ioc.ac.ru Abstract Deep oxidation of volatile organic compounds is one of the most important air pollution control technologies for catalytic treatment of effluent streams from chemical plants and automotive exhaust neutralizers. As a rule, supported catalysts based on noble metals (first of all, platinum) are used in this reaction. Therefore, there is a challenging problem to reduce the cost and increase the efficiency of such catalytic systems. High metal dispersion improves utilization of noble metal. On the other hand, very small metal particles may not by effective in structure-sensitive reactions (e.g. requiring multi-atom surface active sites). For clarification of the relationship between structure-sensitivity of combustion reaction and the structure of combusted molecule we studied an impact of the size of n-alkane molecule (C-chain length) on turnover frequency (TOF) in total oxidation over a series of Pt/Al2O3 containing Pt particles of different sizes ranging from 1 to 11 nm. The specific activity (TOF, s-1, see Fig. 1) of 0.8% Pt/Al2O3 catalysts in the deep oxidation of C1C6 n-alkanes increases with increasing average size of Pt particle from 1 to 34 nm. Further coarsening of the particles insignificantly affects TOF value. It is noteworthy that the range of variations in TOFs values depends on the size of the reacting hydrocarbon molecules. As the platinum particle size increases, the specific catalytic activity increases 34 times in the oxidation of CH4 or C2H6, and by a factor of 2030 in the oxidation of n-C4H10 and n-C6H14. As a result, catalysts with maximum platinum 0.100 dispersion (dPt = 12 nm) exhibit the highest overall activity in the oxidation of small molecules. On the other hand, in the oxidation of longer n-butane and hexane molecules the most active are the catalysts containing larger Pt particles (36 nm), whereas the overall activity of Pt/Al2O3 with high Pt dispersion (10.010 2 nm) is substantially lower.
W sp, s-1

- n-6H14, 172 - n-4H10, 195 - 3H8, 240 - 2H6, 319 - H4, 420
0.001 0 2 4 6 8 10

Financial support by RFBR grant N 08-0301016- is gratefully acknowledged.

d Pt, nm

Fig. 1. Specific activity versus Pt particle size in deep oxidation of C1C6 n-alkanes over 0.8 wt % Pt/Al2O3 catalysts

P56 TEM and SEM characterization and catalytic performance of Pd-Zn/C catalyst for selective acetylene hydrogenation prepared using Pd-Zn(OAc)4(OH2) complex
I.S. Mashkovsky1, A.Yu. Stakheev1, N.Yu. Kozitsyna2, M.N. Vargaftik2, I.I. Moiseev2 N.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky pr. 47, Moscow, 119991, Russia 2 N.S.Kurnakov Institute of General and Inorganic Chemistry RAS, Leninsky pr. 31, Moscow, 119991, Russia E-mail: im@ioc.ac.ru
1

Palladium supported catalysts are known to be effective for the selective removal of acetylene from ethylene feed. Their selectivity can be significantly improved by addition of promoters with respect to suppression of ethane formation. The present study is focused on selective acetylene hydrogenation over a series of novel Zn promoted Pd/C catalysts. The heterometallic Pd-Zn(OAc)4(OH2) complex (I) was used as a precursor for catalyst preparation. XRD analysis [1] revealed that in this complex the palladium atom is strongly linked to the complementary Zn atom. Such structure is favorable for keeping together Pd and Zn atoms during the catalyst reduction, ensuring formation of homogeneous nanoalloyed catalyst. Traditional co-impregnation procedure (by individual solutions of Pd(OAc)2 and Zn(OAc)2.2H2O) was used to prepare Pd-Zn/Al2O3 sample for comparison. It has been shown that Zn significantly improves the selectivity towards hydrogenation to ethylene with little loss in activity. The highest selectivity to ethylene (~90%) was demonstrated by the catalyst prepared from the complex I (Fig. 1). It can be result of Pd-Zn alloy formation detected previously by EXAFS [2] and IR spectroscopy [3]. Data obtained by TEM and SEM techniques also confirmed formation of Pd-Zn bimetallic nanoparticles (Fig. 2). These results clearly demonstrate high potential of heterometallic complexes of Pd with a second metal as catalysts precursors.
100 100

Acetylene conversion, %

Selectivity to ethylene, %

80

80

Pd-Zn
2.06 A 2.06 A

60

60

40

40

20

20

0 20 30 40 50 60 70 80 90 100 110 120 Temperature, C

- Pd/C - Pd-Zn/C from complex (I) - Pd-Zn/C traditional prep.

5 nm

Fig. 1 Acetylene conversion/Selectivity to ethylene Fig. 2 TEM image of Pd-Zn/C vs. temperature. catalyst (from complex I). Acknowledgments The authors kindly thank Dr. Poul Lenvig Hansen, Dr. Alfons Molenbroek, Dr. Fernando Morales Cano and Dr. Charlotte Appel (Haldor Topse A/S) for their help with TEM and SEM analysis, input and fruitful discussions. The authors gratefully acknowledge K.I. Zamaraev International Charitable Foundation for financial support. References [1] N.Yu. Kozitsyna et al., Inorg. Chim. Acta, 359, 2072 (2006). [2] O.P. Tkachenkoet al., Catalysis Letters, 112, 155 (2006). [3] I.S. Mashkovsky et al., Kinetics and Catalysis, 50, 768 (2009).

P57 Sub-nanometer Pt films on top of Pt bimetallic alloys as new oxygen reduction electrocatalysts
Tobias P. Johansson1, Ifan E.L. Stephens1, Alexander S. Bondarenko1, Ib Chorkendorff1. 1 CINF, Institute of Physics, Technical University of Denmark (DTU) E-mail: ibchork@fysik.dtu.dk Abstract The development of low temperature polymer electrolyte membrane fuel cells (PEMFCs) is severely hampered by the fact that the oxygen reduction reaction (ORR) is slow, even using platinum as a catalyst. Recently a new set of platinum compounds, have been identified. These include bulk polycrystalline electrodes of Pt3Sc and Pt3Y, which were experimentally shown to be 1.5-2 and 6-12 times more active than pure Pt, respectively, in the range 0.9-0.85 V [1]. The active phase in these Pt bimetallic systems is a Pt overlayer on top of the bimetallic alloy. There are different ways to produce this overlayer. In [1] the overlayer is formed simply by dissolution of the bimetal upon immersion in to perchloric acid. In this study two different ultra high vacuum routes to forming a Pt overlayer on bulk polycrystalline electrodes of Pt3Sc and Pt3Y are taken. One is to anneal the sample in ultra high vacuum and thereby inducing surface segregation of Pt, like studies known from literature on e.g. Pt3Ni and Pt3Co [2,3]. Another approach is to evaporate a monolayer of Pt on top of the bimetal. Ion Scattering Spectroscopy and X-ray Photoelectron Spectroscopy have been used to analyse the Pt overlayer and the near surface region composition. The surface reactivity is probed by Temperature Programmed Desorption of CO. The ultra high vacuum experiments are then correlated with electrochemical measurements of the oxygen reduction reaction activity. References [1] J.Greeley, I.E.L. Stephens, A.S. Bondarenko, T.P. Johansson, H.A. Hansen, T.F. Jaramillo, J. Rossmeisl, I. Chorkendorff, J.K. Nrskov, Nature Chemistry, 1, 552 (2009). [2] V.R. Stamenkovic, B.S. Mun, K.J.J. Mayrhofer, P.N. Ross, N.M. Markovic, J. Am. Chem. Soc. 128 (27), 8813 (2006). [3] V.Stamenkovic, T.J. Schmidt, P.N. Ross, N.M. Markovic, Journal of Electroanalytical Chemistry, 554-555, 191 (2003).

P58 High-Output Catalyst Development in Energy Research

Olaf Khler, Michael Schneider Chemspeed Technologies, Rheinstr. 32, CH-4302 Augst, Switzerland E-mail: Michael.Schneider@chemspeed.com The generation of clean energy is widely recognized as a key challenge for the future development of mankind. As a result Energy Research is carried out in a variety of areas. Here we will give an overview about High-Output catalyst development namely support preparation and catalyst impregnation carried out together with our partners. Zeolites, Metal-Organic Frameworks and metal oxides supports have been prepared in a high-output automated fashion. As an example the metal oxide supports are precipitated under pH control while continuously feeding acid and base, then aged, filtered, washed and transferred into a storage vial. Afterwards the vessels are automatically prepared to repeat the process several times. Here it delivered up to 3x 20 different, freshly prepared support pastes in 6 hours. V/m pH pH

t/se t/se Fig 1: Single (left) and three consecutive (right) unattended pH controlled precipitation of Bauxit High-Output impregnation methods encompass incipient wetness, excessive liquid, vacuum impregnations as well as impregnation by precipitation. The most abundant of the impregnation methods, the incipient wetness impregnation, serves here as an example for a fully automated, unattended highoutput catalyst development project. 48 different metal/metal impregnation solutions are prepared from the metal salts, acid/base and water. The supports, whether they are powders, spheres or extrudates, are automatically dispensed and homogeneously impregnated to yield precisely the loading of choice.

Fig 2: Catalyst support(Left extrudates, right powder) before and after incipient wetness impregnation. Other High-Output Energy Research solutions comprise Biomass Conversions, Membrane Synthesis for Separation Technologies, Organic Photovoltaics, Hydrogen Storage, Fuel Cell inks and many more.

P59 The oxidation and CO reduction of Pd nano particles: A high pressure x-ray photoelectron spectroscopy study
S. Blomberg1, R. Westerstrm1, J. Gustafson1, J. N. Andersen1, E. Lundgren1, M. Messing2, O. Balmes3, M. E. Grass4, Z. Liu4, H. Bluhm4 1. Division of Synchrotron Radiation Research, Lund University, Lund, Sweden. 2. Solid State Physics, Lund University, Lund, Sweden 3. ESRF, Grenoble, France. 4. ALS, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. The catalytic properties of the Pt-group metals have been studied intensely for many years. Because of the material complexity of a real industrial catalyst, model systems have been developed such as single crystal surfaces under Ultra High Vacuum (UHV) conditions. This effort has resulted in a fundamental understanding of surface reactions by different gases [1]. Therefore, UHV and ex situ techniques have been dominating the investigations and for real catalysis the results may not reflect realistic conditions. Recently, experimental techniques compatible with a higher gas pressure have been developed which allow in situ monitoring of the chemical and structural state of adsorbates and substrates under more realistic pressure conditions [2-5]. In this contribution we report on the in situ oxidation and CO reduction of aerosol deposited Pd particles using High Pressure X-ray Photoemission Spectroscopy (HPXPS) up to pressures of 1 Torr. The Pd particles were deposited by an aerosol method [6] onto a Si wafer with a native SiOx surface layer. The particle size can be controlled to a high degree as confirmed by SEM studies as shown in Fig 1. We used Pd-particles of two different diameters, 15 and 35 nm, and studied the oxidation/reduction reaction.

Figure 1. At the left a SEM image of the pristine 35 nm Pd sample and at the right the size distribution of the particles where a spherical particle shape is assumed. References
[1] G. Ertl, H. Knzinger, and J. Weitkamp, Handbook of Heterogeneous Catalysis. Wiley, New York, 1997 [2] A. Stierle and A. Moelenbroek, MRS Bull. 32, 1000 (2007). [3] E. Lundgren and H. Over, J. Phys. Condens. Matter 20, 180302 (2008). [4] Freund, Surf. Sci. 601, 1438 (2007). [5] D.F. Ogletree, H. Bluhm, E.B. Hebenstreit, M. Salmeron, Nucl. Instrum. Methods A 601 (2009). [6] M. E. Messing, K. A. Dick, L. R. Wallenberg and K. Deppert, Gold Bull., 20, 42, (2009).

P60 Optimizing feed concentrations for lean NOx reduction by HC-SCR over doped AG/AL2O3
Fredrik Gunnarsson, Hannes Kannisto and Hanna Hrelind Ingelsten Competence Centre for Catalysis, Department of Chemical and Biological Engineering, Chalmers University of Technology, SE-412 96 Gteborg, Sweden E-mail: kf03gufr@student.chalmers.se To reduce CO2 emissions in the vehicle industry, engines are shifted to more efficient combustion, i.e. lean-burn engines, which reduces the fuel consumption. However, the lean combustion emissions are similar to those of the diesel engine, which obstruct the NOx reduction in the three-way-catalyst. One possible technique circumventing this problem is selective catalytic reduction using hydrocarbons, i.e. fuel, as the reducing agent (HC-SCR). The technique displays promising results for a variety of hydrocarbons, including fossil fuels and biofuels [1, 2]. In this study silver on an alumina substrate (Ag/Al2O3), with trace amounts of dopant, was evaluated as catalyst. Pure silver-alumina has shown high activity for NOx reduction and introducing a dopant that facilitates partial oxidation of the hydrocarbon may further increase the NOx reduction activity. Introduction of hydrogen to the feed gas is known to shift the NOx reduction window towards lower temperatures [3]. However, a majority of the scientific papers have reported very high hydrogen levels, not applicable in the vehicle industry. In this study, the effects of low levels of H2 in the feed gas and the influence of the NO/NO2 ratio on the NOx reduction activity were investigated. The samples used in this study were prepared by the freeze dried sol-gel method [4] with Ag loading ranging from 2 to 6 wt-%. Some of the silver alumina samples also contained dopant in various amounts. During experiments with temperature ramping, pure 6 wt-% Ag/Al2O3 displayed the highest activity for NOx reduction at low temperatures and the 4 wt-% Ag/Al2O3, with trace amounts of PGM dopant, displayed the highest activity for NOx reduction at higher temperatures. However, the latter displaced the highest activity over the entire temperature range during steady-state experiments. The influence of feed gas composition was studied for this catalyst and, for instance, a NOx conversion of over 50% was achieved at 300 C with 500 ppm H2. It was also shown that substituting some of the NO for NO2 in the feed drastically increases the NOx conversion in the presence of hydrogen.

Figure 1: NOx conversion over temperature during steady-state experiments in a gas flow reactor. GHSV: 33400 h-1 Gas feed: 200 ppm NO, 350 ppm CO2, 10% O2, 1000 ppm H2, 5% H2O (Ar bal.). [1] K. Arve, J. R. H. Carucci, K. Ernen, A. Aho, D. Y. Murzin, Appl. Catal. B: Env. 90, 603 (2009) [2] K. Arve, K. Ernen, M. Snre, F Klingstedt, D. Murzin, Topics Catal., 42, 399 (2007) [3] S. Satokawa, J. Shibata, K. Shimizu, A. Stasuma, T. Hattori, T. Kojima, Chem. Lett. 29, 294 (2000) [4] H. Kannisto, H. H. Ingelsten, M. Skoglundh, J. Mol. Catal. A: Chem., 302, 86 (2009)

P61 Simultaneous production of ethanol based fuel ethers and their corresponding alcohols
1

Kurkijrvi Antti1, Gonzales Rafael2, Linnekoski Juha1 Aalto University, Faculty of Chemistry and Materials Sciences, Industrial Chemistry 2 Universitat de Barcelona, Faculty of Chemistry, Chemical engineering E-mail: Antti.kurkijarvi@tkk.fi

Abstract The interest towards bio components in traffic fuels is steadily increasing. The most common bio component in traffic fuels is ethanol even though its usage as such in cold climates can be problematic. These problems can be evaded if ethanol is etherified. Potential ethanol ethers for traffic fuels are ethyl tert butyl ether (ETBE) and tert amyl ethyl ether (TAEE). In our previous work the effect of water was studied on the kinetics of simultaneous synthesis of TAEE and tert amyl alcohol (TAOH). In this work not only the reactions C5 alkenes are studied, as the reactions of C4 alkenes are also included in to the reaction matrix. This way the focus is on both of the potential ethers simultaneously. The studied reactions are highly affected by water. Water reduces the activity of ion exchange resins because of competing adsorption [1] and dissociation of the active sites [2]. Water also promotes side reactions, which lowers the yield of product ethers even further. Experimental temperatures were 50C, 60C and 70C and the water contents of ethanol were 2000ppm, 11250ppm and 22500ppm. Other sources of water were negligible. The C4/C5 olefin ratio was varied from 0,6 to 1,2 and the olefin/ethanol ratio was 1,15. All reactions were performed at 16 bar with Amberlyst 35 used as the catalyst. The reactions were carried out in a 100 ml stainless steel CSTR reactor equipped with online GC analysis. Water was analysed with Karl Fischer method. Kinfit and Flowbat programs were used in simulations.

Figure: formation rate of ETBE as a function of water content and flow rate. Figures a, b and c represents experimental temperatures of 50 C, 60 C and 70 C respectively From figure it can be seen that all variables have an effect on the formation rate of ETBE. Molar ratio of olefins have the smallest effect as water content and temperature have the most significant effects on the formation rate. Both ethers behaved in a similar fashion. The water content increased side reactions dramatically. For example the hydration of C4 olefin was favoured over etherification of C5 olefin when ethanol contained more than 1 mol-% of water. References [1] Boz N. Dogu T. Murtezaoglu K. and Dogu G. Cat. Today, 100(3-4), 419-424, (2005) Iborra M. Fit C. Tejero J. Cunill F. and Izquierdo J. React. Polym. 21, 65-76, (1993) [2]

P62 New catalysts for dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids

Tim Sthlberga, Sergio Rodrguezb, Peter Fristrupb and Anders Riisagera a Centre for Catalysis and Sustainable Chemistry a,b Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark E-mail: timst@kemi.dtu.dk In recent years, the research on new processes for making renewable chemicals derived from biomass has intensified immensely. In this connection, especially much work has focussed on the selective formation of 5-hydroxymethyl furfural (HMF), which can be formed by dehydration of hexose carbohydrates [1]. HMF is considered to be one of the most important platform molecules of the future chemical infrastructure [2]. The dehydration of fructose in ionic liquids is quite facile and proceeds readily without added catalyst [3], whereas the more economically preferred direct dehydration of glucose to HMF requires a chromium complex catalyst to provide acceptable yield [4]. Chromium-based catalysts are, however, not desirable for large scale production of bulk chemicals due to the negative environmental impact of chromium metal. Consequently, a catalyst replacement containing a more acceptable catalytically active inventory with equal performance is intensively being pursued. In this work we have investigated possible alternatives to chromium chloride catalysts, in particular lanthanide chlorides [5] and boric acid. The studies included testing the catalysts in several ionic liquids as well as conventional molecular solvents. Special focus was given to imidazolium based ionic liquids. Apart from glucose, other carbohydrates such as sucrose, starch and cellulose have also been used as feedstock. In addition to this, our studies have been complemented with DFT calculations and NMR studies with isotop labelling in order to provide insight on the actual mechanism of the reaction. References [1] [2] [3] [4] [5] von Ekenstein, W. Alberda; Blanksma, J. J., Ber. Dtsch. Chem. Ges., 1910, 43, 2355-2361 Werpy, T., Petersen, G., (Eds.) Top Value Added Chemicals from Bio-mass, US Department of Energy, Office of Scientific and Technical Information, 2004, No. DOE/GO-102004-1992, http://www.nrel.gov/docs/fy04osti/35523.pdf Moreau, C.; Finiels, A.; Vanoye, L.; C. J. Mol. Catal. A, 2006, 253, 165-169. Zhao, H., Holladay, J.E., Brown, H., Zhang, Z. C., Science, 2007, 316, 1597-1600. Sthlberg, T., Srensen, M. G., Riisager, A., Green Chem., 2010, 12, 321-325.

P63 Comparison of the Catalytic Activity of Supported Gold Nanoparticles on Ti-oxide and Ti-(oxy)-fluoride
A. Alshammari, A. Kckritz, V.N. Kalevaru, A. Martin Leibniz Institute for Catalysis at the University of Rostock, D-18059 Rostock, Germany E-mail: ahmad.al-shammari@catalysis.de Gold catalysis has continued to attract increasing attention in recent times. In particular, supported gold nanoparticles (AuNPs) can be successfully applied in wide range of oxidation reactions including CO oxidation, alkene epoxidation, and aerobic oxidation of alcohols [e.g. 1]. Generally, the nature of support is believed to play a critical role on the catalytic activity in such reactions. The most common support materials that usually applied for AuNPs are mainly oxide carriers (e.g. Al2O3, TiO2 etc.) [e.g.1]. Recently, metal fluoride based materials are also being applied as effective supports in catalysis but only a very few examples are available in the literature. In this contribution, we present the application of metal oxide and its corresponding metal (oxy) fluoride as catalyst support for AuNPs and compare the influence of such materials on the catalytic performance. For this study, we have selected the oxidation of benzyl alcohol (BA) to benzaldehyde (BAl) as a model reaction. Gold catalysts (1 wt%) supported on (TiO2)-A and (TiF4-x(OH)x)-B, were prepared in two steps. First step deals with the preparation of colloidal AuNPs by the reduction of HAuCl4 in aqueous solution. In the second step, the above-prepared colloidal solution was impregnated separately onto supports A and B. The slurry was stirred for 2 h at r.t., filtered, washed, and then dried at 120 C for 16 h. The dried solids were calcined at 350 C for 5 h in air. In order to compare the catalytic performance of catalysts A and B, it is essential to have a comparable particle size since the catalytic activity of Au catalyst is directly correlated to size and accessible Au surface area. We did not exactly determine the Au surface area, but we have introduced Au surface area specific rates of conversion (RX) and product formation (RBAl) derived from an approximation using a hemispherical model shown in the table. ICP analysis confirmed the loading of Au is comparable. TEM images of catalysts A and B showed a homogeneous gold dispersion with comparable Au particle size distribution. In terms of activity, blank test showed a conversion of approx. 10 %. Between the two, catalyst A displayed high catalytic activity with superior selectivity of BAl. In contrast, sample B Table The physicochemical properties of catalysts A and B and their catalytic showed much less activity and selectivity despite performance its high surface area. This result suggests that the interaction of active phase with the support seems Cat. ICP RBAl SBET- TEM RX to depend on the nature of support used. Using ** ** BAl Au SA 2 (nm) both the catalysts, BAl was the major product, but (%) (wt%) (m /g) some other side products (e.g. benzoic acid, benzyl A 0.93 43 3.4 4.7 4.4 94 benzoate) were also observed. B 0.91 106 3.9 1.9 1.2 67 In conclusion, results have shown that the titania Conditions: BA, 0.29 mol, 0.15 g cat, T = 140 supported catalyst revealed superior performance, C, pO = 5 bar, t = 4 h, 1500 rpm; Au particle 2 whereas oxyfluoride supported solid seems to be size, ** mol/hm2Au less active and selective besides more than doubled BET surface area and same AuNP size as well as Au amount. [1] A. Corma and H. Garcia, Chem. Soc. Rev. 37, 2096 (2008).

P64 Catalytic oxidation of wastewaters under mild conditions

1

Heponiemi, A.1, Rahikka, L.1,2, Lassi, U.1,2, Kuokkanen, T.1 University of Oulu, Department of Chemistry, P.O.Box 3000, FIN-90014 University of Oulu 2 Kokkola University Consortium Chydenius, P.O.Box 569, FIN 67101 Kokkola E-mail: anne.heponiemi@oulu.fi

Abstract The aim of this work is to compare the effectiveness of gaseous (air, oxygen) and liquid (hydrogen peroxide) oxidizing agents in the catalytic oxidation of two different kind of industrial wastewaters. Studied wastewater samples were collected from Finnish food industry and surface plating industry. The major problem in this kind of wastewaters is the high organic concentration of the effluents, and especially in the food industry wastewaters, an unpleasant odour. Supported ruthenium and activated carbon (AC) catalysts have been widely studied and developed in catalytic wet air oxidation (CWAO) but just in few studies they have been applied for real wastewater samples. Activated carbon is also well known for its ability to remove odour from both drinking water and wastewater. In this study, ruthenium catalysts supported on cerium-zirconia mixed oxides and powdered activated carbon are used to study for the removal of organic pollutants from wastewater samples. Especially, in reactions catalysed by AC, the removal of the unpleasant odour was also detected. Catalytic oxidation reactions were carried out in a batch reactor (volume 0.5 L) equipped with a mechanical stirrer. Reaction time was two hours, sample volume 280 mL and the catalyst load 4 g L-1. Reaction temperature varied from 100 C to 150 C and the feeding pressure of gas (air, oxygen) from 3.5 bar to 6 bar. Wet peroxide oxidation (WPO) reactions were carried out at atmospheric pressure and the concentration of the H2O2 varied from 50 to 107 g L-1. Water samples were taken periodically during the oxidation reaction and compositions of the samples were determined as a function of time. Organic concentrations were determined by TOC (Total Organic Carbon) and by COD (Chemical Oxygen Demand). The development of the BOD value (Biological Oxygen Demand) was determined by the manometric respirometric BOD OxiTop method. According to the results hydrogen peroxide seems to be slightly more effective oxidizing agent for these industrial wastewater samples than gaseous oxidants. In non-catalytic WPO (reaction temperature 100 C, H2O2 feed 107 g L-1) the TOC removal after two hours experiment was over 40 % when it was just 10 % in wet air oxidation reaction (temperature 130 C, feeding pressure of air 4.0 bar). Still there is a need to improve efficiencies of the wet oxidation reactions and to abate unpleasant odour although, in reactions catalysed by AC, the odour removal was very effective. Acknowledgements This study was funded by the Maj and Tor Nessling Foundation and Finnish Funding Agency for Technology and Innovation (Tekes) from European Regional Development Fund (EAKR).

P65 In situ DRIFTS investigation of methanol interaction with zirconia-supported noble metal catalysts
1

Sanna Airaksinen1, Andrea Gutierrez1, Reetta Karinen1, Reetta Kaila1,2, Outi Krause1 Aalto University School of Science and Technology, P.O. Box 16100, 00076 Aalto, Finland 2 VTT Technical Research Centre of Finland, P.O. Box 1001, 02044 VTT, Finland E-mail: sanna.airaksinen@tkk.fi

Abstract Methanol is a potential candidate to be used as a hydrogen carrier in the future for fuel cell applications. Hydrogen can be formed from methanol e.g. by steam reforming, partial oxidation, or autothermal reforming. Zirconia-supported mono- and bimetallic noble metal catalysts have been found active in the autothermal reforming of higher hydrocarbons [1] and ethanol [2]. In this study we characterized by in situ DRIFT spectroscopy the surface species formed from methanol on these catalysts in view of their use in steam reforming of methanol. Mono- and bimetallic catalysts based on Pt, Rh, and Pd (0.5 wt-% total metal loading) were prepared by dry impregnation and dry co-impregnation of metal precursors on zirconia support. The samples were reduced in situ with hydrogen in the DRIFTS cell, and the interaction of methanol was studied as a function of temperature from 100 to 500 C. The gaseous products were analyzed on-line by mass spectrometry (MS). In addition, methanol steam reforming experiments were done in a conventional fixed bed reactor. Methanol adsorbed dissociatively forming methoxy groups (OCH3) both on pure zirconia and on the zirconia-supported catalysts at 100 C. Hydroxyl groups were consumed suggesting that methanol reacted with the surface hydroxyls. Adsorbed CO was seen on the metal/zirconia samples. With increasing temperature formate species (HCOO) appeared, and gaseous H2, CO and CO2 were detected by MS. Both the formates and the gaseous products appeared at a lower temperature for the metal catalysts than for pure zirconia. Carboxylate/ carbonate groups were observed at temperatures above 400 C. The results suggest that the decomposition of methanol proceeded through methoxy species, which reacted to formates (possibly via intermediate dioxomethylene species [3]) and decomposed further to gaseous products. Metal species on the catalyst surface facilitated this decomposition. The results will be discussed in relation to further DRIFTS studies and to the activities of the catalysts in methanol steam reforming. Funding by the Academy of Finland is gratefully acknowledged. References [1] R. Kaila, A. Gutierrez, R. Slioor, M. Kemell, M. Leskel, O. Krause, Appl. Catal. B 84, 223 (2008). [2] A. Gutierrez et al., manuscript in preparation. [3] G. Busca, T. Montanari, C. Resini, G. Ramis, U. Constantino, Catal. Today 143, 2 (2009)

P66 Catalytic conversion of mono- and di-saccharides into ethyl levulinate with Brnsted acid ionic liquids
Shunmugavel Saravanamurugan, Olivier Nguyen Van Buu and Anders Riisager Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, DK-2800-Kgs, Lyngby, Denmark. E-mail: ar@kemi.dtu.dk Abstract Today most chemicals are being produced by catalytic transformations of fossil resources such as coal and natural gas. Within a few decades, the availability of these fossil resources will be depleted thus making it imperative to use alternative renewable resources as feed-stock. Carbohydrates are the major renewable resources in biomass and it has become increasingly important to find feasible ways to convert them into useful chemicals such as 5hydroxymethylfurfural (HMF), lactic acid, ethyl levulinate, etc. In this connection, levulinic acid has been recognised as particular important bio-platform chemical which enables as source to produce fuels and other valuable chemicals. To produce levulinic acid, carbohydrates are traditionally being treated with mineral acid [1]. However, a major drawback in this process is tedious work-up producers during the separation stages. Functionalised ionic liquids have emerged as alternative catalysts in many organic reactions due to advantages such as, e.g. - non-measurable vapour pressure, good thermal stability and good phase separation with lipophilic reagents [2]. In the present study, we have studied the conversion of sucrose, fructose and glucose into ethyl levulinate over sulfonic acid functionalised ionic liquids in the presence of ethanol as reactant and solvent. At 140 C fructose was found rapidly dehydrate to form HMF which subsequently reacted with ethanol to from ethyl levulinate with a yield around 70 % within 5 h as shown in Figure 1.
80
Ethyl Levulinate (%)

60
N N OO S O SO3H

40 20 0 0 10

20

30

Time (h)

Figure 1 : Conversion of fructose into ethyl levulinate with [(HO3S-bmim]CH3SO3 ionic liquid at 140 oC References [1] W. W. Moyer, US Patent 2,270, 328 (1942). [2] H. Zhao, J. E. Holladay, H. Brown and Z. C. Zhang, Science 316, 1597 (2007).

P67 Valorisation of cellulose over metal modified mesoporous materials

Mats Kldstrm, Narendra Kumar, Dmitry Murzin Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, bo Akademi University, FIN-20500 bo/Turku, Finland Tel. 3582-2154983, Fax 358 22154479, E-mail: dmurzin@abo.fi Abstract Catalytic upgrading of cellulose into sugars and sugar alcohols has gained a lot of interest in the recent years and several research groups have reported the valorization of cellulose through hydrolytic hydrogenation in aqueous media [12]. In this work we investigated the transformation of cellulose into sugars and sugar alcohols over metal modified mesoporous materials. Cellulose was processed over solid catalysts in an autoclave yielding sugars and sugar alcohols in aqueous media through hydrolytic hydrogenation. The catalytic performance with respect to the catalyst structure, acidity and metal loading was investigated. Ru and Pt on different support were investigated in this catalytic transformation. Birch cellulose with a degree of polymerization of 1900 was dissolved in water and cracked in the hydrolytic transformations. The experiments were done in batch mode in a stainless steel autoclave at 458 K in hydrogen atmosphere at 20 bar initial pressure. All catalysts were reduced for 2 h at 623 K prior to the catalytic testing. The experiments lasted 24 h and liquid samples were periodically withdrawn at different reaction times and analyzed with GC-MS and HPLC. The yield of the transformation products was substantially influenced by the catalyst structure, acidity and metal loading. Five and six carbon sugars were the main products formed along with some sugar alcohols produced through hydrogenation of the corresponding sugars (Figure 1). Detailed reaction network, along with quantification of acidity and selectivity will be given in the presentation.

Xylitol

Sorbitol 5HMF

Figure 1. Sugar alcohols and 5HMF detected with HPLC in the valorization of cellulose.

References [1] A. Fukuoka and P. L. Dhepe, Angew. Chem. Int. Ed., 45, 5161 (2006). [2] D. Weiping, X. Tan, W. Fang, Q. Zhang, Y. Wang. Catal. Lett. 133 167 (2009).

P68 Trends of Fischer-Tropsch Synthesis at Transition metal surfaces

Shengguang Wang, Thomas Bligaard, Jens K. Nrskov Center for Atomic-scale Materials Design, Technical University of Denmark E-mail: spadger@fysik.dtu.dk Abstract Vibration of crude oil prices may cause a shift to coal and natural gas as the feedstock of the fuel industry. Fischer-Tropsch synthesis (nCO + (2n+1)H2 CnH(2n+2) + nH2O) converts synthesis gas into long-chain hydrocarbons, which presents an opportunity to use coal and natural gas. Apart from the engineering and process design of large scale factory and the prices of the feedstock, catalysts are the sole of increasing the efficiency of the reaction. Since the reaction mechanism of Fischer-Tropsch synthesis is unclear with very complex pathway and a wide distribution of products, there is still no microkinetic model based on the properties of catalysts. The present existing models are mostly based on fitted parameters, and they are helpful for engineering and process design. While a theory-based microkinetic model would be helpful for rational catalyst design, but it is challenging. On the other hand, scaling and BEP relations are proved to be useful tools to obtain general trends of catalytic reactions. In this work, we found that they still work for a complex reaction with more than 50 elementary steps.

P69 Renewable building block for plastic industry: Gold-catalyzed oxidation of HMF to FDA in water
Yury Y. Gorbanev1, Sren Kegns1, John M. Woodley2, Claus H. Christensen3 and Anders Riisager1 1 Centre for Catalysis and Sustainable Chemistry, Technical University of Denmark 2 Department of Chemical and Biochemical Engineering, Technical University of Denmark 3 Haldor Topse A/S, Nymllevej 55, 2800 Kgs Lyngby, Denmark E-mail: yyg@kemi.dtu.dk Abstract 5-(hydroxymethyl)furfural (HMF), obtained from biomass, is a possible chemical precursor for the production of 2,5-furandicarboxylic acid (FDA), which has been identified as a key feedstock chemical in future biorefineries [1]. FDA is considered to be a biorenewable building block to form polymers from biomass due to the presence of two carboxylic groups, and therefore an alternative to terephthalic and other acids, produced from fossil resources [2]. Carbohydrates in the form of mono- and disaccharides are readily available from biomass. The hexose type monosaccharides, such as glucose and fructose, can be catalytically dehydrated into HMF. The latter can then be oxidized into FDA via a variety of routes and reaction types. In this context, heterogeneous catalysis is of particular interest due to the ease of catalyst separation and potential reusability [3].

Scheme 1. Highly selective and efficient aerobic oxidation of HMF to FDA in water at ambient temperature in presence of base with supported gold catalyst. A new, sustainable and green catalytic route for the selective oxidation of HMF to FDA with dioxygen was investigated in aqueous basic solution with water as the only by-product [4]. Different supports were screened and TiO2-supported gold nanoparticles were found to oxidize HMF into FDA with 98% yield in water at ambient temperature. References [1] J. T. Werpy, G. Petersen, US Department of Energy, Office of Scientific and Technical Information, No. DOE/GO-102004-1992 (2004) http://www.nrel.gov/docs/fy04osti/35523.pdf. [2] P. Gallezot, Green Chem. 9, 295-302 (2007). [3] A. Boisen, T. B. Christensen, W. Fu, Y. Y. Gorbanev, T. S. Hansen, J. S. Jensen, S. K. Klitgaard, S. Pedersen, A. Riisager, T. Sthlberg and J. M. Woodley, Chem. Eng. Res. Des. 87, 1318-1327 (2009). Y. Y. Gorbanev, S. K. Klitgaard, J. M. Woodley, C. H. Christensen, A. Riisager, ChemSusChem [4] 2, 672-675 (2009).

P70 Imine formation by benign oxidative coupling of alcohols and amines using supported gold nanoparticles as catalyst
Jerrik Mielby, Sren Kegns, Uffe V. Mentzel and Anders Riisager Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby, Denmark E-mail: jjm@vjk.dk Abstract In the past years there has been an increasing interest for efficient heterogeneously catalysed processes for the oxidation of alcohols for production of both fine and bulk chemicals [1]. In particular, considerable effort has been put into the development of aerobic oxidation methods, as oxygen is a cheap and readily available oxidant that produces water as the only by-product. Gold-catalysed aerobic oxidation of alcohols [2] and amines [3,4] is an emerging field in organic chemistry and represents a green and highly atom-efficient alternative to the methods often used in industry. Here, we present our results on the formation of imines by oxidative coupling of alcohols and amines using gold nanoparticles supported on titanium dioxide as heterogeneous catalyst. Initially, benzyl alcohol and hexylamine was used as model substrates for the formation of benzylidene-1-amine. The oxidizing agent was pure molecular oxygen and the reactions were conducted under ambient conditions (room temperature and atmospheric pressure). The effect of adding catalytic amounts of different bases were studied along with the effect of reaction temperature and time. The oxidation procedure was further applied to a number of different primary and secondary alcohols and primary amines and showed that the reaction could be applied to a broad range of substrates, Scheme 1

Scheme 1. Imine formation by oxidative coupling of a primary or secondary alcohol and a primary amine. References G. Franz, R. A. Sheldon: "Oxidation", Ullmann's Encyclopedia of Industrial Chemistry, [1] Electronic Release, 6th ed., chap. 2, Wiley-VCH, Weinheim June 2000. [2] Corma and H. Garcia, Chem. Soc. Rev., 37, 2096 (2008). [3] H. Sum, F. Z. Su, J. Ni, Y. Cao, H. Y. He and K. N. Fan, Angew. Chem. Int. Ed., 48, 4390 (2009). [4] S. K. Klitgaard, K. Egeblad, U. V. Mentzel, A. G. Popvov, T. Jensen, E. Taarning, I. S. Nielsen and C. H. Christensen, Green Chem., 10, 419 (2008).

P71 Photocatalytic liquid phase degradation of ethanol over titanium dioxide catalysts
1

Minna Piril1, Ritva Lenkkeri1, Krisztin Kords2, Ming-Chung Wu2, Riitta L. Keiski1 Univ. of Oulu, Dep. of Process and Env. Eng., P.O.Box 4300, FIN-90014 University of Oulu 2 Microel. and Mater. Phys. Labs, Univ. Oulu, P.O. Box 4500, FIN-90014 University of Oulu E-mail: minna.pirila@oulu.fi

Abstract Photocatalysis is one of the Advanced Oxidation Processes (AOP) which can be used for the purification of harmful compounds e.g. from dilute wastewaters. In this study, the removal of ethanol from aqueous solutions was investigated using two kinds of titanium dioxide photocatalysts, Degussa P25 and TiO2 nanowires. The photocatalytic experiments were carried out in an annular type batch reactor at room temperature using air as an oxidizer. Aqueous solution of 0.25 vol% ethanol and 300-1000 mgL-1 of titanium dioxide catalyst (dispersed into the solution) was irradiated by a UV lamp (Philips Cleo PL-L 36W with intensity maximum at 350-360 nm) placed in the middle of the reactor. After a 30 min dark period the samples were taken periodically, filtered, checked for the pH and analyzed by gas chromatography (GC). The organic carbon contents of the samples were analyzed by TOC (Total Organic Carbon) and by COD (Chemical Oxygen Demand). In all the experiments, pH was found to decrease considerably (from the initial value between 5 and 7 to the value of 4 after five hours illumination) indicating that the reactions had proceeded to the same level of conversion. The maximum ethanol conversion of ~29 % after five hours was reached with the Degussa P25 catalyst while the TOC and COD reductions were 12 % and 17 %, respectively. The TiO2 nanowires seemed not to be quite as effective on the degradation of ethanol (with initial catalyst concentration of 300 mgL-1 the ethanol conversion after six hours was 21% for TiO2 nanowires and 24% for Degussa P25). The TOC and COD reductions in all the experiments indicate that partial mineralization of ethanol had taken place. Acknowledgements This study was funded by the Finnish Funding Agency for Technology and Innovation (Tekes) from European Regional Development Fund (EAKR).

P72 Functionalization of fatty acids in ionic liquids

Mathilde Grau Srensen and Anders Riisager Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark E-mail: mags@kemi.dtu.dk Abstract Expected lack of fossil resources has led to an increasing interest in alternative bio-renewable resources as raw materials for production of fuels and chemicals. In this context, bio-oils are very important as they are found in a number of applications including, e.g. surfactants, fuels, cosmetics and lubricants. Plant oils are particularly useful due to the rapid biomass generation, but also industrial waste products like waste lard or tallow are potential raw materials for generation of useful products. Functional groups, like hydroxyl groups found in e.g. castor oil, can improve properties or give rise to alternative applications [1]. These oils are, however, expensive and the supply is unreliable thus making their use limited. It is therefore of great interest to find a way to synthesise functionalized compounds from alternative, readily available and cheap resources like e.g. rapeseed oil. A possible route to introduce hydroxyl group functionalities is by epoxidation [2], followed by ring-opening to either the monohydroxylated compound or the diol (Figure 1). In this study, the epoxidation of unsaturated fatty acids in ionic liquids have been investigated. The ionic liquid can be adjusted to facilitate desired reactivity as well as solubility properties to allow facile separation of the product phase. The phase behaviour has in the study been predicted using calculations based on the COSMO-RS program.

COOH n m

HO COOH n m n

O COOH m

HO n

OH COO mH

Figure 1: Epoxidation of fatty acids followed by ring-opening to the monohydroxylated or diol product. References [1] J. W. Goodrum and D. P. Geller, Bioresource Technol., 2005, 96, 851-855 [2] K. Wadumesthrige, S. O. Salley and K. Y. S. Ng, Fuel Process. Technol., 2009, 90, 1292-1299

P73 Application of ionic liquid catalysts in the production of biodiesel

Helle Sndergaard, Anders Theilgaard Madsen, Anders Riisager Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark E-mail: hsoe@kemi.dtu.dk Abstract The expected lack of fossil fuels has led to an increasing interest in finding alternatives. One alternative is biodiesel, which consists of fatty acid methyl esters (FAMEs). FAMEs can be synthesized from free fatty acids (FFAs) in an esterfication process or from glycerides in a transesterfication process (Figure 1). The source for FFAs and glycerides can be vegetable oils, animal fats or even used cooking oils. The transesterfication is typically base catalyzed, because it is faster than an acid catalyzed transesterfication, whereas the esterfication only can be performed under acidic conditions. In order to perform the two reactions at the same time an acid catalyst has to be applied, as the FFAs can react with the base to form soap [1]. It is suggested to apply acidic ionic liquids as the catalyst for the production of biodiesel [2]. Figure 1: Biodiesel production from free fatty acids and glycerides. Ionic liquids are organic, low-melting molten salts (mp. below 100 C per definition) which to a large extent can be functionalized according to a specific purpose, e.g. have an acidic moiety which can be catalytically active. Apart from incorporated catalytic activity the ionic liquid can also function as a solvent which can provide phase separation with lipophilic compounds [3]. This dual-functionality makes ionic liquids very feasible for biodiesel production. In this study, different acidic ionic liquids have been synthesized, characterized and applied as both the catalyst and the solvent in the production of biodiesel. References [1] D. Y. C. Leung, X. Wu, M. K. H. Leung, Appl. Energy, 87, 1083 (2010) [2] M. Han, W. Yi, Q. Wu, Y. Liu, Y. Hong, D. Wang, Bioresour technol., 100, 2308 (2009) [3] W. J. Swindal, Clean Techn. Environ. Policy, 6, 149 (2004)

P74 NOx Selective Catalytic Reduction with Hydrocarbons and Hydrogen Effect Over Supported Metallic Catalysts
Roberto Lanza, Lars J. Pettersson KTH -Department of Chemical Engineering and Technology, Stockholm, 100 44, (Sweden) E-mail: lanza@kth.se Introduction The diesel engine emissions limits have become more stringent and the new EURO 6 standards will impose more restrictive limits on particulates and NOx emissions. There exist no efficient catalysts for hydrocarbon selective reduction of NOx (HC-SCR). This process uses hydrocarbons as reducing agents and metallic catalysts to remove NOx from the exhaust gas stream [1]. Experimental In this work we present original results obtained with 3 catalysts, tested in ranges of temperature (200500 C) and gas hourly space velocity (GHSV, 10 00040 000 h-1) typical of diesel engines in real trucks. NO concentration was 500 ppm, C/N ratio ranged between 3 and 12, O2 was always 5%. The catalysts tested were Ag, Pt and Rh supported on alumina (2% metal load). Results and discussion All the catalysts were active and reached very high NO conversion where the maximum conversion ranged from 80 to 100%. Ag was active between 350 and 550 C, achieving complete conversion in a quite wide temperature range. Rh and Pt were active at lower temperatures (200-350C). This is very important since in a truck engine, the exhaust gas temperature can be rather low (during start-up or at truck stop), hence, a catalyst active already at 200250 C is required. Rh and Ag showed a decreased activity when the GHSV was increased from 10 000 to 40 000 h-1, while Pt did not decrease its activity when the GHSV increased. An interesting phenomenon is the effect of co-feeding 2000 ppm of H2. Rh was only slightly affected, but Pt and Ag showed better performances. They reached complete conversion and are very active in a wide range of temperatures. The effect lasted even after H2 was removed. Pt started converting NO already at 50C. The effect of steam was also investigated, finding that at some temperatures it is beneficial for the catalytic activity.
80% 70% 60% Rh Ag Pt

100% 90% 80% 70%

NO Conv [%]

50% 40% 30% 20% 10% 0% 0

NO conv [%]

60% 50% 40% 30% 20% 10% 0%

Pt Rh
0 100 200 300

Ag

100

200

300

400

500

400

500

T in (C)

T in (C)

Figure 1: Typical NO conversions detected without (on the left) and with H2 (on the right). References R. Burch, J. P. Breen, F. C. Meunier, Appl. Catal. B 39, 283 (2002). [1]

P75 Oxidative dehydrogenation of ethane at short contact times

Paul B. Radstake1, Silje F. Hkonsen1,2, Magnus Rnning1, Anders Holmen1,* 1 Department of Chemical Engineering, NTNU, Trondheim, Norway 2 Present address: SINTEF Materials and Chemistry, Hydrocarbon Process Chemistry, Oslo, Norway E-mail: paul.radstake@chemeng.ntnu.no Abstract Ethylene is an important feedstock for many chemical processes, including the production of polymers (e.g. polyethylene, polyvinyl chloride, polystyrene) and high value petrochemical products (ethylene oxide, etc.) [1]. The conventional way for large scale production of ethylene is by steam cracking. A promising alternative to this process, in particular for small-scale operation, could be oxidative dehydrogenation of ethane which offers several advantages such as short contact time and adiabatic operation. However, the favoured side-reaction towards complete oxidation decreases the selectivity dramatically. Several catalysts have been developed for oxidative dehydrogenation of ethane with increased ethylene selectivity, e.g. Pt-Sn alloy systems [2], LaMnO3 perovskite type catalysts [3] and Li/Mg-mixed oxides [4]. The present study is focused on the production of ethylene via oxidative dehydrogenation of ethane using Pt-Sn-impregnated monoliths. Pt-Sn catalysts were supported on cordierite monoliths (Cornings, 62.2 cells/cm2) and tested for the oxidative dehydrogenation of ethane in the presence of hydrogen. Typically, the cordierite monoliths were Al2O3-washcoated prior to impregnation, calcination and reduction. The Pt-Sn catalysts (1 wt% Pt, 2 wt% Sn) were prepared by either sequential impregnation or coimpregnation from Pt(NH3)4(NO3)2 and SnCl2. The oxidative dehydrogenation was performed at 600-900C. The ethane flow was kept constant at 308 NmL/min, the H2/O2 ratio was kept constant at 2 and the total gas flow was always 2000 NmL/min. It has been proposed earlier that the oxidation of additional hydrogen does not influence the ethane dehydrogenation reaction noticeably and only delivers additional heat to the reaction. Indeed, the ethane conversion remains constant with increasing hydrogen content, whereas the ethylene selectivity increases. Additional results concerning H2O- and COx-selectivity and the increase in temperature due to hydrogen oxidation, suggest that the formation of ethylene takes place mainly in the gas phase, but that surface reactions are important in the oxidation to CO/CO2 for the Pt-Sn catalysts. References [1] H. Zimmermann and R. Walzl, in: Ullmanns Encyclopedia of Industrial Chemistry, 12, (WileyVCH, Weinheim, 2003) pp. 531 [2] C. Yokoyama, S.S. Bharadwaj, L.D. Schmidt, Catal. Lett., 1996, 38, 181 [3] T. Seiyama, Catal. Rev., 1992, 34, 281 [4] E. Morales, J.H. Lunsford, J. Catal., 1989, 118, 255

P76 The activating role of H2 on NO oxidation over Ag-Al2O3

Muhammad M. Azis1, Hanna H. Ingelsten2, Derek Creaser1 1 Chemical Reaction Engineering, 2 Competence Centre for Catalysis (KCK), Department of Chemical and Biological Engineering, Chalmers University of Technology, Gteborg, Sweden. E-mail: muhammad.azis@chalmers.se Abstract NOx reduction for lean burn engine exhaust after-treatment is currently an intense area of research. A part of the focus on NOx reduction catalysis has been devoted to the development of Ag-Al2O3 catalysts for HC-SCR. It has been found that the addition of hydrogen considerably promotes NOx conversion over Ag-Al2O3 catalyst and has thus attracted great interest to elucidate the overall reaction mechanism of H2-assisted NOx reduction. It is generally accepted that NO oxidation is one of elementary steps in the overall reaction mechanism of SCR and it has been suggested by some that NO2 is an important intermediate in the NOx reduction mechanism. However, Ag-Al2O3 itself is not an operative catalyst for NO oxidation but addition of H2 has been shown to have a promotional effect on NO conversion [1]. For this purpose, the current study is aimed at investigating the promotional effect of H2 on NO oxidation with a Ag-Al2O3 catalyst. A Ag-Al2O3 catalyst with 5% silver loading was prepared by a sol-gel freeze dried method. The powder was then coated onto a cordierite monolith where the final monolith contained 20% weight of washcoat loading. The NO oxidation activity of the Ag-Al2O3 catalyst was then tested in a flow reactor equipped with FTIR gas analysis. The ramping of temperature from 200C-600C with 5C/min was conducted to evaluate the effect of temperature on NO conversion both with and without the addition of H2. In addition, periodic switching of H2 in and out of the reactor feed at three temperature levels; 250C, 325C and 400C; was also conducted to observe the transient effect of H2 addition. Results from the temperature ramping experiments showed that the addition of hydrogen significantly improved low temperature NO conversion. Furthermore, switching H2 into the reactor feed resulted in a transient overshoot in the outlet NO2 concentration, inferring the direct reduction of surface nitrate species. This observation is in agreement with a DRIFT study of NO oxidation over Ag-Al2O3 [2]. It was also apparent that the quantity of surface nitrate removal tended to decrease with increasing temperature. References [1] Burch R., Breen J.P., Hill, C.J., Krutzsch B., Konrad B., Jobson E., Cider L., Ernen K., Klingstedt F., Lindfors L.-E. Top Catal 30/31: 19-25 (2004) [2] Kannisto H., Ingelsten H.H., Skoglundh M. Top Catal 52:1817-1820 (2009)

P77 Different approaches for the evaluation of reaction mechanisms in microkinetic modeling of methane partial oxidation
M. Surma, D. A. Hoang, D. Chen Dept. of Chemical Engineering, NTNU Trondheim, Norway E-mail: chen@chemeng.ntnu.no Abstract Knowledge of the reaction mechanism of a particular catalytic reaction is a great advantage which can be used for its further investigation. In the field of microkinetic modeling two conditions about the number of elementary reactions need to be fulfilled: It should be high enough to describe the overall reaction without lack of fidelity and small enough to provide reasonable computation time. In this work, two different ways of dealing with elementary steps are shown when the methane partial oxidation catalyzed by nickel is chosen as a case study. In the first case, a large number of different mechanisms is proposed when the algorithm described by Fishtik [1] is employed and they are separately compared to experimental data. In the second case, many elementary reactions are assumed and only those which are with the highest rate at a certain temperature are taken into account. In both cases, the values of adsorption heats and intrinsic activation barriers are estimated by using the unity bond index-quadratic exponential potential (UBI-QEP) method [2], while the preexponential factor of a particular reaction is enumerated by the means of transition state theory [3]. Data for modeling were taken from already published work [4]. All computations were carried out in an application specially developed for the needs of microkinetic modeling, therefore many various models were analyzed in a rather short time. The most likely reaction mechanism was subjected to a further analysis, in which the values of adsorption heats of C, H, O and temperature were parameterized and plotted in graphs. This shows how the results emerging from an experimental work on a certain catalyst (a nickel in our case study) can be transferred to other metal-based catalysts. References [1] I. Fishtik and A. Alexander, Surf. Sci. 430, 1 (1999). [2] E. Shustorovich and H. Sellers, Surf. Sci. Rep. 31, 1 (1998) [3] J. A. Dumesic, The Microkinetics of Heterogeneous Catalysis, ACS, Washington (1993) [4] A. B. Mhadeshwar and D. G. Vlachos, Ind. Eng. Chem. Res. 46, 5310 (2007)

P78 Oxidation with environmentally benign heterogeneous metal catalysts

Ester Eyjolfsdottir, Sren Kegns and Anders Riisager Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby, Denmark. E-mail: eieyj@kemi.dtu.dk Abstract In the past years, there has been a rising demand for efficient heterogeneously catalysed oxidation processes, for e.g. alcohols and aldehydes, for production of both fine and bulk chemicals [1]. So far, these industrially important oxidations have often been carried out using stoichiometric amounts of high-valent inorganic reagents, such as chromate or permanganate, which unfortunately leads to the generation of large amounts of metal waste [2]. In order to avoid waste generation, considerable effort has been put into the development of aerobic oxidation methods using molecular oxygen as the stoiciometric reagent. These methods represent an interesting and highly atom-efficient alternative, as oxygen is cheap, readily available, and an oxidant that produces water as the only by-product. Efficient aerobic oxidation is, however, strongly dependent on a good heterogeneous catalyst which facilitates efficient oxygen activation. The most common catalysts which have been applied for transformations involving aerobic oxidation are based on precious metals, like e.g. Au, Pt and Pd [3,4]. These metals are expensive and scarce. Thus, in order to make such reactions industrially viable it is therefore important to develop new catalyst systems that comprise less expensive and more readily available, environmentally friendly components. In this work, we have evaluated environmentally benign metal catalyst for aerobic oxidation of various oxygenated hydrocarbons. Additionally, we have also examined oxidation reactions of biomass derived substrates into value-added renewable building blocks for chemicals which conventionally are produced from fossil fuels. Such chemicals may find potential use as feedstock in future bio-refineries. References [1] G. Franz, R.A. Sheldon: "Oxidation", Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release, 6th ed., Chap. 2, Wiley-VCH, Weinheim June 2000. [2] R.A. Sheldon, Pure Appl. Chem., 2000, 72, 1233 [3] C.H. Christensen, B. Jrgensen, J. Rass-Hansen, K. Egeblad, R. Madsen, S.K. Klitgaard, S.M. Hansen, M.R. Hansen, H.C. Andersen, A. Riisager, Angew. Chem. Int. Ed. 45, 4648-4651 (2006). [4] A. Corma, S. Iborra, A. Velty, Chem. Rev. 107, 2411-2502 (2007).

P79 Effect of by-product CO on the hydrodeoxygenation of methyl esters

Tuula-Riitta Viljava, Maija Honkela, Eeva-Maija Ryymin and Outi Krause Aalto University, School of Science and Technology, P.O.Box 16100, FI-00076 Aalto E-mail: tuula-riitta.viljava@tkk.fi Abstract Hydrodeoxygenation (HDO) can be used for removal of oxygen from biomass-based fuels to increase their energy content and stability. HDO is carried out in the presence of hydrogen on a catalyst that is conventionally sulfided CoMo or NiMo on -Al2O3 support [1]. The feed can be, for example, vegetable oil or animal fat. The HDO of this type of feed has been studied using methyl and ethyl esters as model components and, for example, the reaction scheme of methyl heptanoate has been studied in detail [2]. In the HDO of methyl heptanoate heptane is the desired end product. CO is produced in the decarbonylation of two of the intermediates, heptanoic acid and heptanal, to hexane [2]. Hexane is a significant by-product (selectivity about 30% with sulphided NiMo [2]) and thus also CO content in the product is considerable. Now experiments were carried out with added CO to study its effect on the catalytic reactions. In order to clearly differentiate the effect of CO on the reactions after CO production has started, the reactant was one of the intermediates, heptanal. Experiments were carried out on sulfided (2 h, 5% H2S in H2) NiMo on -Al2O3 support as catalyst at 250 C and 75 bar total pressure in a batch reactor. CO partial pressures of 0, 0.5 and 2 bar in H2 were tested in the HDO of 3 wt% heptanal in n-dodecane solvent. Five liquid samples were taken during HDO and analysed by gas chromatography. The results showed that CO addition had no clear effect on the hydrogenation of heptanal to heptanol. The dehydration of heptanol to heptene, however, was hindered. Small but clear decrease was also observed in the decarbonylation of heptanal to hexane. Based on earlier studies [3] it can be concluded that CO adsorbs on sulfur-saturated sites on the catalyst surface and competes thus with the dehydration of heptanol and the decarbonylation reactions. This was confirmed with experiments without sulfidation of the catalyst: heptanal reacted to heptanol similarly as with the sulfided catalyst and seems thus not to require sulfided sites. However, the dehydration of heptanol was considerably slowed down in the absence of sulfur. References [1] E. Furimsky, Appl. Catal. A 199, 147 (2000). [2] O.I. Senol, E.-M. Ryymin, T.-R. Viljava and A.O.I. Krause, J. Mol. Catal. A 268, 1 (2007). [3] E.-M. Ryymin, T.-R. Viljava, M. Honkela and O. Krause, oral presentation, Proceedings of the 9th EuropaCat conference, Salamanca, Spain, 2009.

P80 Hydrocracking of Fischer-Tropsch waxes over noble metal catalysts supported on amorphous silica-alumina
Francesco Regali, Magali Boutonnet, Sven Jrs Department of Chemical Technology, KTH, 10044 Stockholm, Sweden E-mail: regali@kth.se Abstract In the Fischer-Tropsch synthesis (FTS), syngas (H2+CO) is converted into long-chain hydrocarbons. It has been shown that the highest diesel yield is given by maximizing selectivity to waxes in the FTS and subsequently hydrocracking the waxes to obtain hydrocarbon chains in the desired range [1]. Noble metal catalysts, e.g. Pt on silica-alumina support, have been shown to give a higher diesel yield when compared to commercial sulfided NiMo catalysts. The reason seems to be a better control of the cracking reactions, limiting overcracking and maintaining a good balance between cracking and isomerization, due to the mild acidity of the support and the high metal dispersion [2]. Pt and Pd bimetallic clusters are interesting as catalysts for mild hydrocracking where Pt-Pd alloys are formed which influence the hydrogen-transfer activity of the metal sites [3]. The aim of this work is to study the behavior of bifunctional metal/acid catalysts consisting of Pt/Pd bimetallic clusters supported on mild acidic amorphous silica-alumina. The catalysts were prepared by the incipient wetness impregnation method from amine metal nitrate precursors: Pt/Pd(NH3)4(NO3)2. Three catalysts with different Pd/Pt molar ratios were compared to pure Pt and pure Pd catalysts. A mechanical mixture of catalyst 1 and 5 (catalyst 6) was tested and compared to catalyst 3 in order to assess the alloy formation.
molarfraction Pt Pd 1 0.80 0.67 0.50 0 0.67 metal loading(wt%) Pt Pd 1 0 0.81 0.11 0.67 0.18 0.51 0.28 0 0.55 0.67 0.18

Cat 1 2 3 4 5 6

Notation 1wt%Pt 4:1Pt:Pd 2:1Pt:Pd 1:1Pt:Pd 0.55wt%Pd 2:1mech.mix

0 0.20 0.33 0.50 1 0.33

The catalysts were characterized by XRD, H2-TPR, CO-chemisorption and N2 adsorption analysis. The results for the activity testing will be presented and discussed. References [1] M.E. Dry, J. Chem. Technol. Biotechnol. 77, 43-50 (2001). [2] D. Leckel, Ind. Eng. Chem. Res., 46 (11), 3505-3512 (2007). [3] S.P. Elangovan, C. Bischof, M. Hartmann, Catalysis Letters, 80, 35 (2002).

P81 Selective Oxidation of Alcohols using Gold/Palladium Bioinorganic Catalysts

K. Deplanche1, M. Merroun2, M. Casadesus3, J. Bennett4, I. Mikheenko1, H. Mounzer4, J. Wood4, G.A. Attard, S3. Solenska-Pobell2 and L. E. Macaskie1 1 School of Biosciences, The University of Birmingham, Birmingham, UK 2 Institut fr Radiochemie, Forschungszentrum Dresden Rossendorf, Germany. 3 School of Chemistry, Cardiff University, Cardiff, UK 4 Dpt of Chemical Engineering, The University of Birmingham, Birmingham, UK E-mail: k.deplanche@bham.ac.uk Abstract The ability of bacterial cells to reduce metallic ions is well known [1, 2]. In some cases, the bioreduction process leads to the generation of metallic nanoparticles (NPs) localised at the cell surface and, in the case of palladium (Pd) and gold (Au), several groups have demonstrated the exceptional catalytic activity of this material in reactions of industrial interest [3, 4, 5]. We report for the first time a facile biochemical method to synthesise bimetallic Au/Pd NPs (BioPd/Au), which exhibit unique properties in the selective oxidation of alcohols to aldehydes. Characterisation of the bimetallic particles using a range of solid state techniques is described. The material shows promising properties in the selective oxidation of benzyl alcohol to benzaldehyde (almond essence) and the synergistic effect of Au/Pd over monometallic preparations is demonstrated. [1] D. R. Lovley, J. Ind. Microbiol. 14, 85-93 (1994). [2] J. R. Lloyd, FEMS Microbiol. 27: 411-425 (2003). [3] N. J. Creamer et al. Catal. Today, 128: 80-87 (2007). [4] W. De Windt, P. and W. Verstraete, Env. Microbiol., 7(3): 314-325 (2005). [5] K. Deplanche, G. A. Attard and L. E. Macaskie, Adv. Mater. Res., 20-21: 647-650 (2007).

P82 Composite of Conducting Polymers, semiconducting oxides and Aligned CNT for Energy Storage
Fan Huanga, Estelle Vanhaeckea and De Chena a Department of Chemical Engineering, Norwegian University of Science and Technology E-mail: fanh@nt.ntnu.no Abstract Renewable energy production and storage is among the most important topics nowadays. Carbon nanostructures have drawn an intensive attention because large aspect ratio, high chemical stability and high electrical conductivity of carbon nanotubes and electro-chemical properties of conducting polymers can contribute to applications such as supercapacitors, batteries, photocatalysts and solar cells [1-3]. The composite made of conducting polymers and CNT in this study is made via in-situ polymerization, either through chemical polymerization or through electro-polymerization. PANI is in-situ polymerized with aligned CNTs supported on foils. In-situ electro-polymerization is carried by using cyclic voltammetry method in the 1M H2SO4 electrolyte with various of sweeping rates. Coating morphology is characterised by SEM and TEM. Chemical composition of the coating is studied by Raman. Thermal properties are examined by TG, DSC carried out in the air gas flow. The SEM and TEM photos confirm the presence and show the morphology of the polymer coating on the CNTs. Raman spectra indicate the chemical composition of the polymer on the CNTs. Response of the composite to the illumination is examined by UV-vis spectroscopy. The UV-vis properties are correlated with the coating amount among the composite. TG tests show the thermal stability of the composites. The charge-discharge property, specific capacitance and electro-chemical stability properties are studied via cyclic voltammetry. This type of composite show the superior potential to be used as solar cell, supercacitor and battery. The semiconducting oxides such as TiO2 is electrochemically deposited on ACNT and doped with noble metals. Its photocatalytic properties are studied. References [1] S. Fan, M.G. Chapline, N.R. Franklin, T.W. Tombler, et al. Science 283 (1999) 512. [2] S. Frank, P. Poncharal, Z.L. Wang, W.A. de Heer, Science 280 (1998) 1744. [3] S.J. Tans, A.R.M. Verschueren, C. Dekker, Nature 393 (1998) 49.

P83 Higher alcohol synthesis from syngas over Molybdenum based catalysts
Robert Andersson, Magali Boutonnet and Sven Jrs KTH (Royal Institute of Technology), Chemical Technology, Teknikringen 42, S-100 44 Stockholm, Sweden E-mail: robean@ket.kth.se Abstract The need for reduction of greenhouse gas emissions, the depletion of fossil energy reserves and an increased fuel demand in the world makes renewable energy sources very attractive. Ethanol is an excellent motor fuel and it is used both as neat fuel and as gasoline additive. Today ethanol is primarily produced by the fermentation technique which limits the use of the biomass feedstock to a few raw materials. The supply of this type of raw materials, like corn and wheat, competes with food production and very large production areas are needed if ethanol is going to be used instead of oil. An alternative route is to gasify the biomass to synthesis gas (H2/CO) and convert the synthesis gas to ethanol (and higher alcohols) using a heterogeneous catalytic process. By this method, virtually all types of biomass feedstock can be used and it makes it possible to increase the alcohol productivity for each ton of raw material. Through the gasification route it is also possible to use undesirable products like various kinds of organic waste. Alkali promoted Co-MoS2 and Ni-MoS2 catalysts experience great alcohol selectivity and high water-gas-shift activity, which makes the catalyst an interesting choice for alcohols synthesis from biomass-derived syngas, which has a H2/CO ratio near 1 [1,2]. The objective of this work, is to design a catalyst with high catalytic activity and high selectivity to ethanol and higher alcohols. To reach this goal, different catalyst preparation methods were investigated to obtain different particle size, promoter, dispersion etc. The effect of reaction parameters was also investigated. Unsupported K-MoS2 catalysts with Ni or Co promoters were prepared by co-precipitation and microemulsion techniques, from thiomolybdate precursors. The catalysts were decomposed under N2 atmosphere and were characterized by TEM, XRD, TPD, chemisorption and BET. CO hydrogenation reactions were performed using a high-pressure 20 ml fixed-bed reactor. Product analysis was carried out on-line with a gas chromatograph (Agilent 7890) equipped with a TCD and two FID detectors. In all measurements a premixed syngas with fixed H2/CO ratio (2:1 or 1:1) and 4% N2 (internal standard) was used. The catalytic tests were carried out at high pressure (50-100 bar), temperatures ranging from 320370C and space velocities between 2400-24000 ml/g/h. All tested catalysts show high alcohol selectivity (50-95%, CO2-free) and high water-gas-shift activity (near equilibrium). Selectivity and conversion is strongly affected by pressure, temperature and space velocity. CO conversion increases quite much with increasing pressure and the H2/CO ratio should be kept relatively low to reduce hydrocarbon formation and increase higher alcohol formation. A H2/CO ratio near 1:1 has shown to be suitable. Alcohol selectivity decreases and hydrocarbons selectivity increases with increasing CO-conversion. Catalysts prepared by the microemulsion technique produce smaller, mono dispersed metal particles, compared to the catalysts prepared with the co-precipitation technique. Effect on selectivity and conversion with particles prepared with different techniques as well as characterization results will be presented.

50 40
(CO2-free)

Selectivity (C%)

30 20 10 0 0 5000 10000 15000 20000 25000 GHSV (ml/g cat/h)

MeOH EtOH CH4 PrOH

Figure 1: Product distribution over an unsupported K-Ni-MoS2 at various space velocities (GHSV). H2/CO=1, Ptot=91 bar and T=340C. References [1] Iranmahboob, J., Toghiana, H.,Hill, D.O. Appl.Catal. A: General 247, 207 (2003). [2] Li, Y., Wang, R., and Chang, L. Catal. Today 51, 25 (1999).

P84 Development of nanostructured electrodes on foils

Estelle Vanhaecke, Fan Huang, De Chen, Magnus Rnning Department of Chemical Engineering Norwegian University of Science and Technology E-mail: estelle.vanhaecke@chemeng.ntnu.no Abstract Carbon nanotubes are studied for their potential applications in catalysis and energy storage, particularly electrochemical supercapacitors with high power and high energy density applications [1, 2]. They present a great interest as electrodes for many applications including fuel cells, solar celles, electrocatalysis and chemical/biological sensing. As a matter of fact, the outstanding properties of individual CNT and their anisotropic structure make the CNTs forest particularly attractive. The forest is synthesized by the CCVD process, where a selective growth on various substrates is possible due to the cost-effectiveness stability and the repeatability of the process. The growth of aligned CNTs on a substrate was achieved using an hydrocarbon source gas such as C2H4 or C2H6. The catalyst deposition technique used for this study was the decomposition of an organometallic catalyst precursor located in the oven just before the foil. The inlet mixture was first composed by nitrogen and hydrogen in order to obtain the reduced state of the catalyst precursor. After reaching the temperature synthesis fixed at 750oC, the carbon source was introduced and maintain during the desired synthesis time. Plasma oxidation was done on the CNTs forest in order to eliminate the carbonaceous residue and to create oxidized surface on the CNTs. This oxidation is particularly useful in order to deposit on the CNTs other media such as polymers, nanoparticles or even films according to the desired application. Different characterization techniques such as SEM, Raman were used for optimizing the parameters. The capacitance measurements were realized by using a galvano/potentiostat with a -electrodes set up and was compared with the capacitance of non-supported CNTs pellets. References [1] Y. Murakami, S. Chiashi, Y. Miyauchi, M. Hu, M. Ogura, T. Okubo, S. Maruyama, Chemical Physics Letters. 385 (2004) 298-303. [2] H. Wang, J. Feng, X. Hu, K.M. Ng, J. Phys. Chem. C. 111 (2007) 12617-12624.

P85 Production of biomass derived synthesis gas by catalytic steam reforming

Espen Standal Wangen, Amin Osatiashtiani, Edd A. Blekkan Dept. Chemical Engineering, Norwegian University of Science and Technology E-mail: wangen@chemeng.ntnu.no Abstract Synthesis gas (syngas), a mixture of H2 and CO, is an intermediate in the production of several fuels and chemicals. The syngas may be produced from fossil resources like natural gas and coal. However, the concerns associated with the increase in atmospheric CO2 concentration make biomass a possible source in the future. Syngas from biomass can be produced by gasification, followed by multiple physical and chemical cleaning steps. This gas conditioning is necessary due to the wide range of contaminants present in the raw product gas. The product gas from a biomass gasifier will also contain unconverted hydrocarbons that should be converted in order to maximise the syngas yield. The focus of this project was the conversion of such hydrocarbons by catalytic steam reforming. Conventional nickel catalysts are widely used in steam reforming processes. However, these materials are rapidly deactivated by sulphur compounds. In this project, three novel, monolithic non-nickel catalysts were compared and investigated in terms of steam reforming activity and stability. Steam reforming reactions were carried out in a tubular steel reactor with three different monolithic catalysts (ceramic, 400 cpsi, different metals and washcoat). The reactant gas in these experiments was a model gas whose composition was as follows: CH4: 12 v-%, C2H4: 5 v-%, CO: 23 v-%, CO2: 25 v-%, H2: 35 v-%. N2 was added as internal standard. Water was fed by a liquid pump. The composition of the product gas from the steam reforming was analysed by means of a micro-GC. Reactions were carried out at temperatures from 620 to 720 C and atmospheric pressure. The steam:carbonorganic ratio in the experiments ranged from 3 to 10. In order to investigate the effect of tars (defined as aromatic hydrocarbons higher that benzene) toluene (light tar) and 2-naphthol (heavy tar) was added as model tar compounds in some of the experiments. The catalysts proved to be active at the chosen conditions. CH4 is the more stable component in the system, and close-to-equilibrium conversion was achieved. As for the higher hydrocarbons, full conversion was achieved. The results indicate that no catalyst deactivation occurred, but stable operation of the reaction was maintained during the first 50 hours. No pressure drop was observed over the monolith during the experiment, but some carbonaceous material was observed by visual inspection of the monolith after reactions.

P86 In situ deactivation study of the rhenium behaviour in Co-Re Fischer-Tropsch catalysts
Alexey Voronov1, Nikolaos E. Tsakoumis1 Magnus Rnning1, yvind Borg2, Erling Rytter1,2 and Anders Holmen1 1 Department of Chemical Engineering, NTNU, NO-7491 Trondheim, Norway 2 Statoil R&D, Research Centre, Postuttak, NO-7005 Trondheim, Norway E-mail: voronov@chemeng.ntnu.no Abstract A Co-Re catalyst supported on -alumina has been studied using XAS spectroscopy at Fischer-Tropsch reaction conditions in order to obtain information about Re promoter effects and their behaviour during the activation period and the reaction itself. It has been reported by Das et al. [1] that small amounts of rhenium added to the cobalt catalyst decreased the reduction temperature of cobalt oxide but did not significantly alter the actual Co dispersion. A comprehensive study on Re promotion effect during reduction was done by Jacobs et al. [2] who claimed Re remains present on the surface as isolated Re atoms in intimate contact with the cobalt metal cluster. The state of Re at Fischer-Tropsch reaction conditions (18 bar, 210 C) has not been studied before using X-ray absorbtion spectroscopy. Data obtained by XAS spectroscopy at the Re LIII edge concludes that Re is incorporated in the Co clusters. Futhermore, the rhenium atoms distort the local Co hcp strucure. This is most liely because of the larger atomic radius of Re.
15 10

k 3*chi(k)

5 0 3 -5 -10 -15 5 7 9 11 13 15

k( )

-1

Figure 1: Fourier-filtrated experimental data (red curve) after 10h of reaction run compared with theoretical model of a Re-Co cluster (blue curve). A useful Co-Re interaction model was found for describing the Re behaviour in the Co-Re catalyst during FT reaction. During 24 hours of reaction no significant changes were detected in Re-Co coordination number. Re is not completely reduced, and a fraction is present in low oxidation states. The oxidation state of Re seems to be stable during FT reaction and is not the reason for catalyst deactivation. References [1] T. K. Das, G. Jacobs, P. M. Patterson, W. A. Conner, J. Li, B. H. Davis, Fuel 2003, 82, 805. [2] G. Jacobs, T. K. Das, P. M. Patterson, J. Li, L. Sanchez, B. H. Davis, Applied Catalysis A: General 2003, 247, 335.

P87 Conversion of oxygenates over zeolite H-ZSM-5: Towards direct production of hydrocarbon fuels from biomass
Uffe V. Mentzel1,2, Martin S. Holm1,2 1 Centre for Catalysis and Sustainable Chemistry, Technical University of Denmark 2 Haldor Topse A/S, DK-2800, Kgs Lyngby, Denmark E-mail: uvm@kemi.dtu.dk Abstract Due to environmental concerns and diminishing fossil resources, development of new processes for production of hydrocarbon fuels from alternative sources such as biomass is of immense importance. Direct conversion of biomass over zeolite H-ZSM-5 through catalytic fast pyrolysis has been published recently [1], and also the conversion of bio-oil obtained from pyrolysis of biomass has been investigated [2]. In both cases extremely rapid deactivation is observed due to coke deposition on the zeolite. Here we present zeolite catalysed conversion of model compounds such as glycerol which can be directly derived from biomass with focus on deactivation and catalyst lifetime. Figure 1 shows the conversion capacity of the zeolite (H-ZSM-5) before complete deactivation for different concentrations of glycerol in methanol. Dilution in methanol has a distinct beneficial effect on the conversion capacity.

Figure 1: Catalyst conversion capacities for conversion of different concentrations of glycerol in methanol (H-ZSM-5, 370 C, WHSV 8 gg-1h-1) Over 20 different compounds obtainable from biomass (phenols, acids, esters, ketones, aldehydes) have been converted over zeolite H-ZSM-5 in different concentrations in methanol (typically 10%). The incorporation of the additive in the hydrocarbon fuel product has been confirmed through isotopic labelling experiments performed with 13C-labelled compounds. References [1] [2] T. R. Carlson, J. Jae, Y-C. Lin, G. A. Tompsett, G. W. Huber, J. Catal. 270, 110, (2010) G. Gayubo, B. Valle, A. T. Aguayo, M. Olazar, J. Bilbao, Energy & Fuels, 23, 4129 (2009)

P88 The effect of hydrothermal aging on the structure and activity of three-way catalysts
Oxana Korsak1, F. Wen2, M. Santhosh Kumar1, Paul Hug1, Jrgen Giesshof2, Anke Weidenkaff1, Davide Ferri1 1 Empa, Lab. for Solid State Chemistry and Catalysis, CH-8600 Dbendorf, Switzerland 2 Umicore AG & Co. KG, D-63403 Hanau-Wolfgang, Germany E-mail: davide.ferri@empa.ch Abstract Three-way catalysts for the exhaust treatment of gasoline and natural gas fuelled vehicles are an important component of present emission control solutions as they are able to simultaneously abate noxious pollutants such as CO, NOx and hydrocarbons [1]. Despite their resistance to severe changes in temperature and in reaction conditions (cyclic operation of =1), these catalysts are subject to aging which typically causes loss of activity on mileage manifesting in increasing emission levels. A facet of this process is hydrothermal aging causing by the combination of high temperature and the presence of water in the car exhaust. The activity of the metal nanoparticles is typically greatly affected by the harsh conditions encountered in the catalytic converter. This study should assist to rationalize strategies against thermal aging effects. As prepared and hydrothermally aged (700C and 1000C, 16h, 10% H2O, 10% O2) catalysts (2 wt.% M/Al2O3, where M is Rh, Pt, Pd) have been chosen to systematically study the aging effect of the precious metal component on an alumina support. The catalysts have been characterized using BET, XRD, TEM, DRIFT, CO chemisorption and EXAFS and their three-way catalytic activity has been measured with respect to the abatement of CO, NO and propene. The characterization results indicate that the response of the three noble metals to hydrothermal aging is different. Pt and Pd form larger particles with increasing temperature but the oxidation state is different: Pt is reduced whereas PdO is the major species on Pd/Al2O3. Three-way activity is variously affected by these states. Information on structural changes induced by aging involving Rh can only be obtained using advanced in situ methods. Aging mostly affects the oxidation state of Rh [2]. With increasing aging temperature an oxidic phase is formed that is resistant to reduction and at 1000C Rh migrates into Al2O3. The high levels of N2O in the sample aged at 700C confirm how oxidic Rh is responsible for N2O formation. The activity of the sample aged at 1000C is inferior and selectivity to N2O very low because of the incorporation of the Rh component within the support. Combined in situ DRIFT and XAS studies with simultaneous MS analysis provided structural-activity relationships under NO-CO cyclic operation. Increasing of aging temperature does not only cause changes in the population of surface species during NO-CO cycles but also deteriorates the ease of the red-ox processes. References [1] M.V. Twigg, Appl. Catal. B: Environmental 70, 2 (2007). [2] C.P. Hwang, Q. Yhu, Catal. Today 51, 93 (1999).

P89 Reaction mechanism of Ru based catalysts on methane partial oxidation

Roberto Lanza1, Paolo Canu2, Sven Jrs1 KTH -Department of Chemical Engineering and Technology, Stockholm, 100 44, (Sweden) 2 DIPIC-Universit degli Studi di Padova, Padova, Italy E-mail: lanza@kth.se Experimental One of the catalysts was Pt-Ru (50:50 w/w, 1% total load) supported on Al2O3/CeO2/ZrO2. In this work we identify and quantify the reactions occurring during the global CPO process and describe the mechanism [1]. Other Ru catalysts are also being tested (Ru/TiO2, Ru/CeO2, Ru/SiO2) and the influence of the calcination atmosphere is also investigated. During the CPO activity tests, a CH4/O2/N2 mixture (3.4/1.7/94.9 % by vol.) is fed to the reactor.
1

Results and Discussion Figure 1 shows CH4 and CO2 conversions detected with Ru-Pt catalyst. The catalyst is active for dry reforming (DR) but also small amounts of water were produced (other reactions are involved). Feeding CH4 and H2O allowed verifying that steam reforming (SR) is also catalyzed (Figure 1, right). The reaction gives the highest conversions at the lowest GHSV, confirming that the H2O formed in the first complete combustion step leads to CPO products if enough residence time is allowed for steam reforming to occur. Direct and reverse water gas shift reaction tests were run. The catalyst was active and both the reactions approached equilibrium. The other catalysts prepared are not fully tested yet, but some CPO tests gave indication of the same reaction mechanism. Different calcination atmospheres (reducing and oxidizing) were employed for these catalysts, this resulting in different performances.
100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% 400 CH4 - 26 000 1/h CO2 - 26 000 1/h CH4 - 53 000 1/h CO2 - 53 000 1/h CH4 - 93 000 1/h CO2 - 93 000 1/h CH4 eq CO2 eq
100% 90% 80% 70% 60%

CH4 25 000 1/h CH4 100 000 1/h H2O 50 000 1/h CH4 equil

CH4 50 000 1/h H2O 25 000 1/h H2O 100 000 1/h H2O equil

C * i (% )

C *i (% )
450 500 550 600 650 700 750 800

50% 40% 30% 20% 10% 0% 300

Tin (C)

400

500

600

700

800

Tin (C)

Figure 1: (left) CH4 and CO2 trends during DR tests. (right) CH4 and H2O trends during SR tests. Ru/SiO2 calcined in in air was active and selective, with indications of the indirect mechanisms. When supported on CeO2, Ru was active both after calcination in H2 and in air atmosphere. Concerning the mechanism, again production of CO2 and H2O indicates a first step of complete combustion, therefore an indirect mechanism. Conclusions All the tests run proved that the reaction on Ru-Pt catalyst goes through the combustion and reforming mechanism (CRM). CO2 and H2O are formed and the catalyst is active in DR and SR. Also the other catalysts give clues of following the indirect mechanism. References L. D. Schmidt, M. Huff, Catal. Today 21 443 (1994). [1]

P90 Structure sensitivity of NO, N2 and O2 dissociation over low-indexed transitionmetal alloy surfaces
Wei Guo, Jens K. Nrskov, and Thomas Bligaard CAMD, DTU, Building 307, DK-2800 Kgs. Lyngby, Denmark E-mail: weiguo@fysik.dtu.dk

Abstract The dissociation process of diatomic molecules is one of the fundamental steps in many important chemical reactions such as e.g. NO decomposition, N2 fixation and various oxidation reactions. Here we present density functional theory (DFT) calculations for NO, N2 and O2 dissociation over low-indexed surfaces of transition metals and alloys. Linear Brnsted-Evans-Polanyi (BEP) relations between the transition-state (TS) potential energy and the dissociative chemisorption energy are obtained. The BEP relations of different facets show strong structure sensitivity with respect to the dissociation process. Such geometric effects combined with additional electronic effects provide opportunities for the computational design of more active and selective catalysts for certain reactions.

P91 Scaling relations for intermediates for ammonia synthesis on nanoparticles

1

Jakob G. Howalt, Anthony Goodrow, Jens Nrskov, Thomas Bligaard Center for Atomic-scale Materials Design, Technical University of Denmark, DK 2800 Kgs. Lyngby, Denmark E-mails: s052881@student.dtu.dk and bligaard@fysik.dtu.dk

Abstract In today's world, an energy-efficient method is desired for chemical synthesis of ammonia (NH3) from molecular nitrogen (N2) in air. Over 100 million metric tons of NH3 are produced annually, with 80% used as fertilizer. Currently, ammonia synthesis is achieved by the Haber-Bosch process, which is energy-intensive due to the required high temperature and pressure. In the past several years, numerous studies have examined ammonia synthesis and offer excellent insight into the challenges faced with developing new catalytic materials for this reaction. It has been shown in previous studies that ammonia synthesis is very structure sensitive on metals[1]. Furthermore, it has been shown that a similar reaction, CO oxidation, can be performed at low temperature on transition state nanoparticles[2,3]. The present work suggests that nanoparticles can be used for N2 reduction because of the increased activity of these under-coordinated metal nanoparticles. We have investigated the reaction intermediates for the dissociative and associative mechanism on ten transition metal M12 nanoparticles and developed similar scaling relations compared to stepped metal surfaces. References [1] S. Dahl, et al. Phys. Rev. Lett. 83, 1814 (1999), 83, 1814. [2] D. Goodman et al. Top. Catal. 71, 14, (2001). [3] T. Jiang, et al. Jour. of Phys. Chem. C 113, 10548 (2009)

P92 Structure-activity relationships of Pt/Al2O3-based diesel oxidation catalysts

Alexey Boubnov1,2, Sren Dahl3, Erik Johnson2, Anna Puig Molina1, Sren Bredmose Simonsen1,3, Fernando Morales Cano1, Stig Helveg1, Lived J. Lemus-Yegres1 1 Haldor Topse A/S, Nymllevej 55, DK-2800 Kgs. Lyngby, Denmark 2 Nano Science Center, University of Copenhagen, DK-2100 Kbenhavn , Denmark 3 CINF, Danish Technical University, DK-2800 Kgs. Lyngby, Denmark E-mail: alexeyboubnov@gmail.com Introduction Diesel engines for light-duty vehicles are an attractive alternative to petrol engines because of their better fuel economy. On the other hand, exhaust aftertreatment systems are necessary to decrease toxic emissions. A diesel oxidation catalyst (DOC) is responsible for catalysing the oxidation of carbon monoxide (CO) and uncombusted fuel to CO2 and water, and the oxidation of nitric oxide (NO) to nitrogen dioxide (NO2). In this work we investigated the effect of the particle size on the catalytic activity of the DOC as well as the Pt oxidation state under working conditions. Experimental Catalyst samples with mean Pt particle size in the interval 1-10 nm were prepared; the particle size was tuned by varying postsynthesis thermal ageing conditions. The samples were characterised by transmission electron microscopy (TEM) and hydrogen chemisorption. The activity for CO and NO oxidation was measured in a model diesel exhaust (O2:CO and O2:NO ratios of 100). Furthermore, in situ X-ray absorption spectroscopy (XAS) provided information on the Pt oxidation state and atomic coordination sphere. Results Bench testing of the DOC samples showed that Pt particles of 2-3 nm were superior for CO oxidation, while NO oxidation was optimised over Pt particles of >4 nm. This suggests different reaction pathways for the two reactions. XAS revealed that the Pt was partially oxidised under the given reaction conditions, altogether suggesting that the susceptibility of Pt particles to become oxidised is a determining factor for the activity of the DOC. Previous studies of CO oxidation at near-stoichiometric O2:CO-ratios have shown that CO reduces the Pt surface at low temperatures [1, 2], which is not the case in this work.

TEM image of a Pt/Al2O3 catalyst studied in this work.

References [1] F. J. Gracia et al., J. Catal. 220, 382 (2003) [2] J. Singh et al., Angew. Chemie Int. Ed. 47, 9260 (2008)

P93 Heterogeneously Catalyzed Selective Hydrogenation Reactions In Supercritical Carbon Dioxide

Nikolai E. Musko1, Jan-Dierk Grunwaldt1,2 DTU, Chemical Engineering Department, Kgs. Lyngby, Denmark 2 KIT, Institut fr Technische Chemie und Polymerchemie (ITCP), Karlsruhe, Germany E-mail: nm@kt.dtu.dk, grunwaldt@kit.edu
1

Introduction Hydrogenation reactions over heterogeneous catalysts provide access to a wide variety of bulk and fine chemicals. Hydrogenation of C=C double bonds in unsaturated aldehydes gives industrially important saturated aldehydes which are frequently used as fine chemicals in different reactions. The present study aims at coupling them with a second reaction, aldol condensation, which provides chemicals used as solvents, flavours, additives for different purposes, etc. [1]. Particularly interesting is the combination of both in one step (see e.g. ref. [3]). We present here the investigation of new types of bifunctional heterogeneous catalysts for selective hydrogenation of unsaturated aldehydes towards saturated aldehydes and subsequent aldol condensation of the latter both in conventional solvents and supercritical CO2 (scCO2). Heterogeneous catalysis combined with the use of scCO2 gives a number of opportunities [2]. Gas-like properties of scCO2 significantly decrease heat and mass transfer limitations in the process and relatively high density and solubility (liquid-like properties) allow using it instead of conventional solvents. Use of cheap, non-flammable and environmentally benign CO2 makes both the chemical and separation processes easily tuneable, which is a very attractive tool for improving their performance. Results A number of palladium catalysts on activated carbon with different metal loading have been prepared and tested in hydrogenation reactions with unsaturated aldehydes such as acrolein, 2-butenal, 2-pentenal, 2-hexenal, etc. both in conventional solvents and scCO2. In its turn, different types of carriers have been tested in aldol condensation reactions with a number of corresponding saturated aldehydes (propanal, nbutanal, n-pentanal, n-hexanal, etc.). All the experiments have been carried out in a batch cell together with phase behavior observations. The catalysts were further characterized using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), transmission electron spectroscopy (TEM), and thermal programmed desorption (TPD) to give insight into the catalyst structure. The hydrogenation step occurred under relatively mild conditions (50C, H2:substrate = 2:1 mol) with satisfactory conversion and selectivity. Better performance has been observed for all the reactions in scCO2 compared to those in the conventional liquid solvent. Aldol condensation reactions in carbon dioxide showed high conversion and selectivity as well. The next step of the work is now devoted to developing and optimization of the bifunctional catalysts for the one-step process. Phase modeling and theoretical calculations will be performed for better understanding of the process. Advanced association models, e.g. PC-SAFT or CPA, which can describe scCO2 and polar hydrogen bonding compound will be used [4]. References [1] J. G. Stevens, R.A. Bourne, M. Poliakoff, Green Chem., 11, 409 416, 2009 J.-D. Grunwaldt, R. Wandeler, A. Baiker, Catal. Rev. Sci. Eng. 45, 1, 2003 [2] [3] T. Seki; J.-D. Grunwaldt; A. Baiker, Chem. Commun., 3562 3564, 2007 [4] I. A. Kouskoumvekaki, G.M. Kontogeorgis, Fluid Phase Equil., 241 344, 2006

P94 Oxidation of 5-hydroxymethylfurfural with homogeneous Cu(I) catalysts

Thomas S. Hansen and Anders Riisager Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark E-mail: thomh@kemi.dtu.dk Abstract The still increasing demand for sustainable CO2 neutral technologies has recently caused heavily research efforts in this field. One approach is to substitute fossil based transportation fuels with ones based on a sustainable feedstock - namely biomass. Another approach is to make sustainable chemicals from biomass resonated from the fact that the fuels for the transportation sector can be substituted by alternative carbon free resources whereas carbon containing chemicals can not. An important compound that is obtained relatively easy from biomass feedstocks is 5hydroxymethylfurfural (HMF), which is formed by the consecutive dehydration of fructose [1]. This compound can potentially act as a bio-based precursor for many industrial valuable chemicals and thereby substitute a great number of chemicals with fossil origin [2]. One compound that is obtainable from the oxidation of HMF is 2,5-furandicarboxylic acid (FDA) a terephthalic acid (TPA) analogue which can be utilized in polyester production as replacement for TPA [3]. In this work, we have studied the catalytic oxidation of HMF using Cu(I) and 2,2,6,6tetramethylpiperidine-1-oxyl (TEMPO) with air as the stoichiometric oxidant and by use of Cu(I) with tert-butylperoxide as oxidant (Figure 1).
Fructose

O Cu(I) / t-BuOOH HO

O TEMPO / Cu(I) / Air O

5-Hydroxymethylfurfural

O HO

O OH

2,5-Furandicarboxylic acid

2,5-Furandicarbaldehyde

Figure 1: The reaction path from fructose to HMF and further to either 2,5-furandicarboxylic acid (FDA) or 2,5-furandicarbaldehyde. References [1] T. S. Hansen, J. M. Woodley, A. Riisager, Carbohydr. Res. 344, 2568 (2009). [2] A. Corma, S. Iborra, A. Velty, Chem. Rev. 107, 2411 (2007). [3] A. Boisen, T. B. Christensen, W. Fu, Y. Y. Gorbanev, T. S. Hansen, J. S. Jensen, S. K. Klitgaard, S. Pedersen, A. Riisager, T. Sthlberg and J. M. Woodley, Chem. Eng. Res. Des. 87, 1318 (2009).

P95 Towards a generally applicable density functional including van der Waals interactions
Jess Wellendorff and Thomas Bligaard CAMD, Department of Physics, Technical University of Denmark E-mail: jesswe@fysik.dtu.dk Abstract Density functional theory (DFT) is today a main tool within theoretical catalysis and surface science. DFT using exchange-correlation (xc) functionals within the generalized gradient approximation (GGA) has broven to work well for describing strong interactions within mole-cules as well as between adsorbates and reactive surfaces. However, it is also widely agreed that GGAs fail to correctly account for the far weeker van der Waals (vdW) interactions. These long-ranged and non-local correlation interactions, often grouped into hydrogen bon-ding and dispersion interactions, are very inportant in biological matter such as DNA. They are also responsible for the physisorption of benzene molecules on noble metal surfaces [1]. The van der Waals density functional (vdW-DF) takes vdW interactions into account by introducing a non-local correlation to be used in conjunction with local (LDA) correlation and GGA exchange. This scheme has proven useful for treating archetypical van der Waals systems such as rare gas dimers and the interactions between graphene sheets [2]. The agre-ment of vdW-DF with high-level theory is often, however, no more than semi-quantitive. Also, application of the vdW-DF to bulk transition metals yields significantly overestimated lattice constants and far too small cohesive energies, as compared to both experiments and GGA-DFT calculations. This limits the usefulness of the vdW-DF in studies of transition metal catalyzed reactions. We have traced to origin of this problem to the use of LDA corre-lation instead of the highly popular GGA correlation. Several research groups are currently looking for the optimum form of GGA exchange to be used in the vdW-DF scheme [3]. However, very limited attention has ben paid to the correlation part of the functional. I will present results from recent studies, where we show that reintroducing GGA correlation instead of LDA correlation leads to several advantages. First of all, the agreement with high-level coupled cluster calculations for the s22 database of vdW bonded dimers and complexes is immediately improved, yielding a mean-absolute-deviation only half that of vdW-DF. Secondly, vast improvements are found for bulk metals where both lattice constants and cohesive energies are closer to experimental values than the corresponding GGA-DFT value. Finally, we find that DFT calculations including van der Waals interactions and GGA correlation yields molecular atomization energies compara-ble to those obtained within pure GGA-DFT. These developments challenge the conventionel view that the non-local vdW-DF cor-relation term must be paired with LDA correlation, and lay a new possible path towards a generally applicable density functional that preserves or even improves on GGA results and at the same time quantitavely accounts for van der Waals interactions. References [1] J. Wellendorff, T. Bligaard et al., Top. Catal., (2010) [2] D.C. Langreth et al., J. Phys.: Condens. Matter 21, 084203 (2009) [3] J. Klimes et al., J. Phys.: Condens. Matter 22, 022201 (2010)

P96 Interrelation between Fe3+ and Cu2+ cations in the Cu-Fe-Beta catalyst for selective catalytic reduction of NOx by ammonia as evidenced by ESR
Dmitry E. Doronkin1, Alexey V. Kucherov1, Alexandr Yu. Stakheev1, Arkady L. Kustov2, Marie Grill2 1 Zelinsky Institute of Organic Chemistry RAS, 119991, Leninsky Prosp. 47, Moscow, Russia 2 Haldor Topse A/S, P.O. Box 213, Nymllevej 55, DK-2800 Lyngby, Denmark E-mail: st@ioc.ac.ru Abstract Fe-Beta is one of the most effective catalysts for selective catalytic reduction (SCR) of NOx by ammonia. On the other hand Cu-containing zeolites possess remarkable low-temperature activity in NH3-deNOx. Hence it may be interesting to combine copper and iron active sites in Beta-zeolite in order to improve its catalytic activity in NH3-deNOx. 0-1.5 wt.% Cu were loaded on 0.15 wt.% Fe-Beta using the incipient-wetness impregnation. The catalysts were hydrothermally treated and tested under conditions of NH3-deNOx. It was found that low-temperature activity (k175) increased over Cu-0.15Fe-Beta and Cu-H-Beta catalysts with the increase of Cu content. The observed catalyst activity at 175 C correlates with Cu content and corresponding ESR signal for Cu2+. This finding implies that Cu2+ cations are main active species responsible for low-temperature activity. However the situation is different when analyzing changes in the catalyst activity at high temperatures where the catalyst activity is determined mainly by Fe3+ active sites. At 385 C catalyst activity (k385) decreases linearly with decreasing concentration of Fe3+ as evidenced by intensity of ESR signal at g = 4.27. Simultaneously, ESR signal of Cu2+ increases. The decrease in the population of active Fe3+ cations is evidently caused by its displacement by Cu2+ ions, which is a thermodynamically favored process. Since Cu-Beta is also active in NH3-deNOx the catalyst activity at 385 C does not drop to zero. Instead, with decreasing concentration of active Fe3+ species, it reaches a level which is characteristic for 1.5%Cu-Beta catalyst. k , cm /g/s k , cm /g/s
385 3 175 3

90

Thus ESR study revealed competitive replacement of isolated tetrahedral Fe3+ ions by Cu2+ ions in cationic sites of the zeolite upon copper loading on Fe-Beta followed by calcinations. This leads to a minor deNOx activity gain in low-temperature region and significant loss of activity at high temperatures. D. Doronkin is grateful to Haldor Topse A/S for financial support in the framework of Ph.D. student support programme.

20

70
10

50
0

30 0 0.5

Cu loading, %

1.5

Figure 3. Decrease of activity of residual Fe (k385) in CuH-Beta with Cu loading and appearance of activity from Cu (k175 and k385 when Cu loading > 1%).

, solid line - k385; , dashed line - k175

P97

A study of the catalytic activity of ZrO2 in bio-oil production under nearcritical water conditions
D. F. Aarup,a J. Becker, a M. Glasius,a S. Villadsen,a S. B. Iversen,b B. B. Iversena* a) Dept. of Chemistry and iNANO, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C. b) SCF Technologies a/s, Smedeholm 13B, DK-2730 Herlev * E-mail: bo@chem.au.dk Abstract A novel facility for the production of bio-oil from biomass has been intensively tested [1]. The feedstock used was in all cases DDGS - a co-product from the ethanol industry, which is normally dried and sold as cattle feedstock [2]. Bio-oils were produced within 15 minutes at near-critical water conditions as a hydrothermal liquefaction [3] with and without the use of heterogeneous ZrO2-catalyst. Special attention was drawn towards the role of the catalyst with respect to oil yield and chemical composition. Another important point is the reproducibility of products, especially when handling real biomasses, and this was investigated by performing an extended run of 23 sequential experiments during a 24 hour period. Clear effects of the catalyst could be seen with regard to oil yield, which increased from 15 wt% to 28.1 wt%, but no clear indication of chemical changes in the bio-oil were observed according to GC-MS measurements. The extended experimental run highlighted the trend seen in previous experiments, and it is clear that the catalyst needs an initialization period before maximum oil yields are obtained. This complicates the comparison of short experimental series, since the uncertainty from the catalyst initialization is profound.

Figure 4: Photo of the reactor

From the industrial (and scientific) point of view it is of interest to maximise the oil yield, and therefore experiments were also carried out with doubling of the amount of catalyst. The oil yields did not significantly increase with increasing catalyst quantity. 1. 2. 3. Becker, J.T., L. L.; Aarup, D. F.; Villadsen, S. R.; Glasius, M.; Iversen, S.B.; Iversen, B.B., A high temperature, high pressure facility for controlled studies of catalytic activity under hydrothermal conditions. Energy & Fuels, 2010. 24: p. 2737-3746. Tiffany, D.G.M., R. V.; De Kam, M. J., Economics of biomass gasification/combustion at fuel ethanol plants. American society and agricultural and biological engineers, 2009. 25(3): p. 391400. Peterson, A.A., et al., Thermochemical biofuel production in hydrothermal media: A review of sub- and supercritical water technologies. Energy & Environmental Science, 2008. 1(1): p. 3265.

P98 ELECTROCATALYSIS ON MODEL SURFACES: OVERLAYERS, NEAR-SURFACE ALLOYS AND SURFACE ALLOYS OF Cu-Pt
Alexander S. Bondarenko,1 Francisco J. Perez-Alonso,1 Rasmus Frydendal, 1 Anders K. Jepsen, 1 Brian P. Knudsen, 1 Ifan Stephens,1 Wei Tang,1 Anna S. V. Gasque,1 Lone Bech,1 Federico Calle-Vallejo,2 Jan Rossmeisl,2Ib Chorkendorff.1 1 CINF, 2CAMD Department of Physics, Technical University of Denmark (DTU). E-mails: ifan@fysik.dtu.dk, lbech@fysik.dtu.dk, ibchork@fysik.dtu.dk In order to accelerate the development of low temperature fuel cells, new catalysts are required to improve the efficiency of these devices. Bimetallic Pt-based alloys hold promise as catalysts for key electrocatalytic reactions, in particular the oxygen reduction reaction (ORR), and the methanol oxidation reaction (MOR) [1]. Herein, we demonstrate how a Pt (111) single crystal can be tailored towards these reactions, by alloying its surface with Cu. Our investigations encompass Cu-overlayers on Pt, Pt-Cu surface alloys and Pt-Cu near-surface alloys, as depicted on Fig. 1. Recent surface science studies have shown that such structures exhibit unique properties that are markedly different from pure metals or bulk alloys [2, 3]. The catalysts were characterised in-situ using electrochemical measurements in aqueous solutions of HClO4. The surface composition of these alloys was characterised ex-situ using X-ray photoelectron spectroscopy and ion scattering spectroscopy. Density functional theory calculations are used to support and interpret our results at a microscopic level. The experiments performed on single crystals are compared and correlated to similar measurements taken on Pt-Cu nanoparticles.

Fig. 1. Illustration of the Pt-Cu near surface alloy and surface alloy [2]. [1] H.A. Gasteiger, J. Garche, Fuel Cells, in: G. Ertl, H. Knoezinger, F. Schueth, J. Weitkamp (Eds.) Handbook of Heterogeneous Catalysis, Wiley-CPH, Chichester, 2008, pp. 3081-3120. [2] K.J. Andersson, F. Calle-Vallejo, J. Rossmeisl, I. Chorkendorff, J. Am. Chem. Soc., 131 (2009) 2404-2407. [3] J. Knudsen, A.U. Nilekar, R.T. Vang, J. Schnadt, E.L. Kunkes, J.A. Dumesic, M. Mavrikakis, F. Besenbacher, J. Am. Chem. Soc., 129 (2007) 6485-6490.

P99 New Mesoporous Silica Supported Nickel Catalysts for Biomass Conversion
Steven Fiddy1, David Lundie1, Simon Hodgson2, Maria Olea2 and Wei Wang2 1 Hiden Analytical Ltd, 420 Europa Boulevard, Warrington, WA5 7UN, UK 2 School of Science and Technology, University of Teesside, Middlesbrough TS1 3BA, UK E-mail: sfiddy@hiden.co.uk Introduction Organic waste through biomass conversion can be used for energy production and the synthesis of a variety of chemicals. One of the synthesis routes is via biogas to syngas catalytic conversion, by CO2 reforming of CH4. For the methane reforming reaction, all metals of the VIIIA group on a large variety of supports have been studied. Ni shows good catalytic activity, especially when well dispersed on the support. Experimental Characterisation. Temperature programmed reduction (CH4-TPR), oxidation (O2-TPO), and reaction (TPRx CH4:CO2 = 1.5:1) experiments were performed using a CATLAB microreactor MS system (Hiden Analytical, UK) on fresh and in situ reduced Ni catalysts. Heating rates were 10oC min-1. In situ reduction was performed under a H2 flow by heating to 550oC at 10oC min-1 and holding at this temperature for 1 hour. XRD data were obtained on a Bruker D8 diffractometer. Results and Discussion The TPR results shown in Figure 1 show the 11% Ni samples to have high activity with CH4 reduction occurring at around 580 C. Figure 2 shows the TPRx results of a prereduced 11% Ni sample. Here, conversion of CH4 + CO2 2H2 + 2CO occurs at around 400 C with complete conversion of the CO2 occurring at around 700 C.
800 700 600
Temperature CO2 O2 CO H2O CH4 H2

1.8x10 1.6x10 1.4x10 1.2x10

-7

800 700 600

Temperature H2 CH4 H 2o CO O2 CO2

6.0x10

-7

-7

5.0x10

-7

-7

Temparature / C

Temperature / C

-7

500 400 300 200 4.0x10 100 0 0 20 40 60 80 100 2.0x10 0.0 1.0x10 6.0x10
-7

500 400 300 200

4.0x10

-7

Pressure / Torr

Pressure / Torr

3.0x10

-7

-8

2.0x10

-7

-8

1.0x10 100

-7

-8

0 0 30 60 90

0.0

Time / Mins

Time / Mins

Figure 1. 11%Ni CH4TPR

Figure 2. TPRx 11%Ni (prereduced)

Conclusions Methane activation occurred at relatively low temperatures. TPReaction demonstrate the high activity and selectivity of these catalysts. Structural and textural properties of the mesoporous support are retained independent of the Ni loading. Ni is well dispersed inside the mesopores.

P100 Reactivity of Heterogeneous Catalyst by DFT and Parameterized-Model Studies: Towards S tolerant Bimetallic Structures
Nilay Inoglu*, John R. Kitchin Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Avenue Pittsburgh, PA 15213-3890 USA *E-Mail: ninoglu@andrew.cmu.edu The surface electronic structure is the key factor determining the activity and selectivity of many late transition metals. Understanding how the surface electronic structure varies due to alloying and adsorbate coverage effects is essential to understanding the variations in chemical reactivity among adsorbate covered alloy surfaces. We have developed a simple tight-binding model that accounts for changes in the surface electronic structure due to the presence of adsorbates and/or due to alloying. Here, we present a tight-bonding approach parameterized by a database of density functional theory calculations to model the effects of simple adsorbates (C,N, O and S) and alloying on the surface dbands of the late transition metals. The model includes the combined effects of electronic and geometric contributions as well as the coverage dependences in adsorption energies. We discuss how our model could be used in conjunction with DFT calculations to rapidly screen a broad range of structures to identify surfaces with desirable electronic and thus chemical properties. As an application, our model is used as a screening tool over 484 transition metal based binary alloy combinations to determine surface structures with enhanced S resistivity.