Catalysis Norskov 05 15 02

Heterogeneous Catalysis
Opportunities and challenges

J. K. Nrskov
Center for Atomic-scale Materials Physics
Technical University of Denmark
norskov@fysik.dtu.dk
Challenges
Societal needs
Developing the basic understanding
Opportunities
Designing at the nano-scale
Challenges I
Dream reactions waiting for a catalyst:
Jens Rostrup-Nielsen: XVII Sympsio Iberoamericano de Catlisis, July 16-21 , 2000
Challenges II
Dreaming on .
Heterogeneous catalysts for assymmetric synthesis

Photolytic water splitting (hydrogen economy)
Biomimetics, synthetic enzymes
Non-thermal processes in general
(e.g. electro- and photocatalysis)

See: E. Derouane, CATTECH 5, 226 (2001)
Challenges III
The science of heterogeneous catalysis:
A comprehensive scientific basis
Much has been done
Much more is needed (oxides, size effects,
photocatalysis, electrocatalysis, relation to
homogeneous and enzyme catalysis )
Making the insight useful!

The ultimate test
Opportunities
- design at the nano-scale
Rational catalyst design
- Discovery on the basis of insight
Data-driven methods
- Accelerated discovery by access to
large amounts of data
Bio-inspired catalysis
Rational catalyst design

1. What determines the catalytic
activity/selectivity/lifetime ?
2. How can we affect it?
- We have tremendous new possibilities
Ammonia synthesis
N2+3H2 2NH3
Ozaki and Aika, Catalysis 1 (Anderson and Boudart, Ed.)
Ammonia synthesis over Ru

Ru(0001)
step
Logadottir, Nrskov
Steps do everything
Au decorates steps:
Hwang, Schroder, Gunther, Behm,
Phys. Rev. Lett. 67, 3279 (1991)
Dahl, Logadottir, Egeberg, Larsen, Chorkendorff, Trnqvist, Nrskov, Phys.Rev.Lett. 83, 1814 (1999)
The Brnsted-Evans-Polanyi relation
Logatottir, Rod, Nrskov, Hammer, Dahl, Jacobsen, J. Catal. 197, 229 (2001)
Calculated ammonia synthesis rates

400 C, 50 bar, H2:N2=3:1, 5% NH3
Ru
10 1
Os
TOF(s-1)
10 0
Fe
10 -1
Co
10 -2
10 -3
Mo
Ni
10 -4
10 -5
-0.8
-0.4
0.0
0.4
0.8
[E-E(Ru)](eV/N2 )
Logatottir, Rod, Nrskov, Hammer, Dahl, Jacobsen, J. Catal. 197, 229 (2001)
Interpolation in the periodic table
Jacobsen, Dahl, Clausen, Bahn, Logadottir, Nrskov, JACS 123 (2001) 8404.
Interpolation in the periodic table
Measured ammonia synthesis rates

400 C, 50 bar, H2:N2=3:1
Data driven methods

High throughput screening
Direct testing of many catalysts, fast,
efficiently
Data mining
Correlating catalytic activity/selectivity/
durability to descriptors that can be tabulated
H. Toulhoat and P.
Using DFT calculations Raybaud

Workshop Catalysis from
First Principles Vienna
in the search of prospective
02/02
catalysts
The object of the game
Find sets of descriptors {Dik} of solid materials Mi ,
and a mathematical model F such that Aij being the
Turn Over Frequency of Mi as catalyst for the reaction
j at operationg conditions C j one has:
Aij M i , C j F Dik ,C j
Identify ranges of Dik that maximize F

Screen Databases of Materials Properties before
screening real materials
Better if one descriptor is sufficient, but do not take it
for granted
Much better if F has a sound physical basis
H. Toulhoat and P.

02/02
catalysts
E MC YY/PAW/GGA/SP (kJ/mol)
Periodic Trends for E MC in Fm-3m (NaCl) carbides

160
140
120
100
80
60
40
20
0
Ti
Sc
Zr
Cr
Mn
Fe
Co
Ni
Cu
Hf
Ta
Nb
Mo
Tc
Ru
Rh
La
Pd
Ag
Re
Os
Ir
Pt
Au
H. Toulhoat and P.

02/02
catalysts
Onset of
dissociative
chemisorption
as MC bond
strength
Adsorption of C2H4 100K
increases
: di- bound
bound
Sc
Ti
Zr Nb Mo Tc Ru Rh Pd Ag
La
Hf
Ta
R = 0,894
500
Re Os
Ir
Pt Au
W
Cr
y = 1,9625x - 29,758
400
R2 = 0,791
300
Fe
Ni
Ru
Pt (Diss.)
200
Rh
Au
Pd
Cu
Pt(molec)
Ag
Cr Mn Fe Co Ni Cu
W
Ta
y = 6,267x - 287,99
100
: No ads.
600
Qads exp. C2H4/M (kJ/mol)
E MC @ Fm-3m
carbides is
rather
consistent with
simple
chemisorption
models
0
0
20
40
60
80
100
120
E MC YY (@NaCl/PAW/GGA/SP) (kJ/mol)
140
H. Toulhoat and P.

02/02
catalysts
The
experimenta
l Alloying
effectsis
correctly
predicted
-1
Rate in Hydrogenation of C6H6 (s )
1,E+05
1,E+04
TOF@30C (M/Al2O3
Brunelle et al., 1977)
V thor.
1,E+03
Pt
1,E+02
Ni
Ir3Re
Co
Os
Re3Ir
Ir
Ir3Cu
Re
Ru
Cu3Ir
1,E+01
Pd
Cu
1,E+00
10
12
14
16
18
20
22
E MC YY (kCal.mol-1)
24
26
28
30
Getting data/descriptors
Structure (in situ)

Spectroscopy (in situ)
Surface thermochemistry
Calculations
There is a large need for systematic data

- and for good descriptors
Structure-activity Correlation
Hydrodesulfurization of thiophene
HDS activity
(x102/mol/g/h)
1.5
10
Topse, Clausen, Massoth

Hydrotreating Catalysis, Science and Technology
(Anderson and Boudart (Eds.), Springer (1996).
0.5
0
1
2
3
Number of Co edge atoms
(x1020/g catalyst)
Descriptors from spectroscopy

CO TPD shift
Core level shift
Goodman and Rodriguez, Science 279 (1992) 897
Single crystal microcalorimerty

Cu/MgO
Ag/MgO
Pb/MgO
Larsen, Starr, Campbell, Chem.Thermodyn. 33, 333 (2001)

Brown, Kose, King, Chem. Rev. 98, 797 (1998).
Descriptors from
DFT
Correlation between adsorption

energies and activation barriers
and the d-band center
Mavrikakis , Hammer, Nrskov

Phys. Rev. Lett. 81, 2819 (1998)
CO tolerance of Pt alloy anodes for PEM fuel cells

Measured overages of CO on the alloy electrodes
with 100 ppm CO/H2
1,0
M. Watanabe et al., Phys. Chem. Chem. Phys. 3 (2001) 306
1-co
0,8
0,6
0,4
0,2
0,0
Pt
Calculated changes in CO adsorption energy
-d, eV
S. Gottesfeld et al.,
J. Electrochem. Soc. 148 (2001) A11.
0,8
1,5
0,6
1,0
0,4
ECO , eV
1,0
2,0
0,5
0,2
0,0
0,0
-0,5
-0,2
Pt Fe Co Ni Cu Ru Rh Pd Ag Ir
Substrate M
Au
Christoffersen, Liu, Ruban, Skriver, Nrskov, J.Catal. 199, 123 (2001)
How can the d-band center be changed?

Calculated d band shifts:
Overlayer
Host
Ruban, Hammer, Stoltze, Skriver, Nrskov, J.Mol.Catal. A 115, 421 (1997)
Methane activation
Transition state for CH4
dissociation on Ni(211)
Bengaard, Rostrup-Nielsen, Nrskov
Methane activation on Ni/Ru

5e-7
Thermal dissociation of CH4 at T = 530 K

4e-7
3e-7
2e-7
1e-7
0
0
Ni Coverage [ML]
Egeberg, Chorkendorff, Catal. Lett. 77, 207 (2001)
Lessons from biology

Catalysis at ambient temperature and
pressure
Extreme selectivity
Direct coupling of energy into the important
reaction coordinate (non-thermal catalysis)
Nitrogenase
N 2 8H 8e
nitrogenase
ATP
2NH 3 H 2
ADP AlF4-
complex formation
FeP (MgATP) 2+ MoFeP

nucleotide
replacement
k1
k -1
FeP (MgATP) 2 MoFeP
MoFe protein
ATP cleavage
electron transfer
FeMo cofactor
Fe protein
reduction
FePox(MgADP) 2 + MoFeP
k3
k -3
4Fe-4S cluster
P-cluster
k2
k4
Fe protein
FePox (MgADP, Pi ) 2 MoFeP
complex dissociation
Burgess, Lowe, Chem. Rev. 96, 2983 (1996)

Schindelin, Kisker, Schlessman, Howard, Rees, Nature 387, 370 (1997)
N2 hydrogenation on FeMoco
Rod, Nrskov
JACS 122, 12751 (2000)
The Fe Protein cycle

MoFe protein
Fe protein
ATP
1)
FeMoco P-cluster
4Fe-4S cluster
2)
3)
ADP
HPO 24
4)
See also: Spee, Arendsen, Wassnik, Marrit, Hagen, Haaker, FEBS Lett. 432, 55 (1998)
Comparing the FeMoco and Ru(0001)
Rod, Logadottir, Nrskov

J.Chem.Phys. 112, 5343 (2000)
Status
Well developed basic understanding theory-experiment

Beginning to be able to use it directly in catalyst design
Some activity-descriptor correlations
Host of new in situ methods for catalyst characterization
New very powerful screening methods
We have a starting point which is radically different from
the situation 5 or 10 years ago!
Moving forward
More basic understanding theory-experiment
Integration of the conceptual framework for
heterogeneous, homogeneous and enzyme catalysis
More systematic data (descriptors)
Better synthesis methods
Better coupling of catalyst design and process engineering
INTEGRATION
Promoting development
An integrated approach:
Experiments, models
Synthesis
testing
characterization
Theory

Catalysis Norskov 05 15 02

Uploaded by

Copyright:

Available Formats

Catalysis Norskov 05 15 02

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Catalysis Norskov 05 15 02

Uploaded by

Copyright:

Available Formats

Heterogeneous Catalysis

Opportunities and challenges

Jens Rostrup-Nielsen: XVII Sympsio Iberoamericano de Catlisis, July 16-21 , 2000

Heterogeneous catalysts for assymmetric synthesis

See: E. Derouane, CATTECH 5, 226 (2001)

Making the insight useful!

Rational catalyst design

Ozaki and Aika, Catalysis 1 (Anderson and Boudart, Ed.)

Ammonia synthesis over Ru

The Brnsted-Evans-Polanyi relation

Calculated ammonia synthesis rates

Interpolation in the periodic table

Interpolation in the periodic table

Measured ammonia synthesis rates

Data driven methods

Using DFT calculations Raybaud

Identify ranges of Dik that maximize F

Using DFT calculations Raybaud

Periodic Trends for E MC in Fm-3m (NaCl) carbides

Using DFT calculations Raybaud

Qads exp. C2H4/M (kJ/mol)

Using DFT calculations Raybaud

Rate in Hydrogenation of C6H6 (s )

Structure (in situ)

There is a large need for systematic data

Topse, Clausen, Massoth

Descriptors from spectroscopy

Core level shift

Goodman and Rodriguez, Science 279 (1992) 897

Single crystal microcalorimerty

Larsen, Starr, Campbell, Chem.Thermodyn. 33, 333 (2001)

Correlation between adsorption

Mavrikakis , Hammer, Nrskov

CO tolerance of Pt alloy anodes for PEM fuel cells

M. Watanabe et al., Phys. Chem. Chem. Phys. 3 (2001) 306

Calculated changes in CO adsorption energy

Christoffersen, Liu, Ruban, Skriver, Nrskov, J.Catal. 199, 123 (2001)

How can the d-band center be changed?

Ruban, Hammer, Stoltze, Skriver, Nrskov, J.Mol.Catal. A 115, 421 (1997)

Bengaard, Rostrup-Nielsen, Nrskov

Methane activation on Ni/Ru

Thermal dissociation of CH4 at T = 530 K

Lessons from biology

FeP (MgATP) 2+ MoFeP

FeP (MgATP) 2 MoFeP

FePox (MgADP, Pi ) 2 MoFeP

Burgess, Lowe, Chem. Rev. 96, 2983 (1996)

The Fe Protein cycle

Comparing the FeMoco and Ru(0001)

Rod, Logadottir, Nrskov

Well developed basic understanding theory-experiment

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.