Zeolites: Composition and Structures

NPTEL – Chemical Engineering – Catalyst Science and Technology
Lecture 36
Zeolites
Composition and structures
Zeolites are crystalline aluminosilicates with pores of molecular dimensions. The general
formula for a zeolite is Mx/n[(AlO2)x(SiO2)y].mH2O. M is the metal or hydrogen cation of
valency ‘n’ occupying the exchangeable cationic sites on zeolite framework. AlO2 and
SiO2 are fundamental units sharing oxygen ions to form tetrahedral AlO4 and SiO4
building blocks for zeolite unit cell. Since silicon ion has +4 and Aluminium has +3
charges there is an overall negative charge on the aluminosilicate framework. The
cationic charge of the metal or hydrogen ion balances the negative charge on the
aluminosilicate framework.
Aluminosilicates are formed by polymerization of SiO4 and AlO4 tetrahedra to form sheet
like polyhedral. The polyhedra forms cubes, hexagonal prisms and truncated octahedral.
These 3D tertiary building blocks in turn are arranged regularly to form a superstructure
inside which pores and supercage exists. Each supercage is characterized by a window
size aperture which can block entry of sufficiently large molecules. This is known as
sieve effect. The zeolite structures have pores oriented in one, two or three directions
leading to 1D, 2D, 3D structures. Structures of zeolite X and A is shown in Fig 1.
Zeolite X Zeolite A
Fig 1. Schematic diagram of zeolites structures
Zeolites are classified based on their pore diameter and ring size. Among aluminosilicate
zeolites 3A, 4A, 5A and erionite containing 8 number of rings have pore diameters in the
range of 3-5 Å. ZSM 5 and mordenite with 10 and 8 rings respectively have pore
Joint initiative of IITs and IISc – Funded by MHRD Page 1 of 56

diameters in range of 3-5 Å. On the other hand, faujasite X andY have 12 rings with
larger pore diameter of 7 - 8 Å. Aluminophosphates (ALPOs) have significantly extended
range of pore sizes. ALPOs containing 12 rings have pore diameter of 10 Å while 18 ring
ALPOs have pore diameter of 10-15 Å.
Table 1. Compositions of common zeolites per unit cell
Zeolite type Na AlO2 SiO2 H2 O
Zeolite A 12 12 12 27
Zeolite X 86 86 106 264
Zeolite Y 56 56 136 264
ZSM-5 9 9 87 16
Mordenite 8 8 40 24
Preparation of zeolites
Zeolites are synthesized by crystallization from reactive forms of silicon, aluminum,

0
sodium, sodium hydroxide and organic template at 90-180 C and 1-10 atm pressure.
The pH is maintained higher than 10. Seed crystals are added to the reactor to initiate the
crystallization process. Typical crystallization time varies in the range from 16-36 h.
Organic template is added to facilitate formation of pores and supercages. Typically
organic template is an organic amine or alkyl ammonium compound. Crystallization of
the gels proceeds around the template molecular mold producing the porous network. The
synthesis of various zeolites is achieved by varying the synthesis conditions such as
temperature, pH, crystallization time, order of mixing and amount of Si, Al, Na, and H2O.
Laboratory preparation of NaX Zeolite and ZSM-5 zeolite is discussed below.

Preparation of ZSM-5 zeolite [1]

Aluminum nitrate and colloidal silica are added to a stirred mixture of tetrapropyl
ammonium bromide and sodium hydroxide solution to give a hydrogel. Then, the
hydrogel was transferred to a stainless-steel autoclave with a Teflon lining and placed in
an oven for appropriate periods. After the completion of crystallization under
autogeneous pressure, the autoclave is cooled down, samples are washed and dried at 120
0
C for 24 h. Finally, the sample is calcined at 500 0C for 16 h to remove the organic base
occluded in the zeolite framework, protonated in hydrochloric acid solution at room
temperature for 24 h, and then again dried at 393 K.
Preparation of NaX Zeolite [ 2]

The sodium silicate and sodium aluminate are prepared separately. The silica gel and
aluminum isopropoxide is used as starting materials for silicon and aluminum
respectively. The sodium silicate is prepared by adding silica gel, sodium hydroxide, and
deionized water to a plastic beaker stirred until the solids are completely dissolved. The
sodium aluminate solution is prepared simultaneously by adding aluminum isopropoxide,
sodium hydroxide, and deionized water. The mixture is stirred below 80 0C until the
solids are dissolved to form a clear gel and the mixture is cooled to room temperature.
Then the aluminate solution is added to the silicate solution with additional amount of
water. The final mixture is stirred until homogenous and then placed in an oven for 24h at
90 0C. After 24 h, the mixture is cooled to room temperature giving white zeolite crystals.
The crystals are washed thoroughly with water, filtered and air-dried.
Properties of zeolites
a. High surface area and ordered pore structure

High surface area and ordered pore structure of zeolites result in their unique adsorption
properties. Zeolites are characterized by large surface area because of its highly porous
nature. The surface area of zeolites is in the range of 600-800 m2/g. As a result of high
surface area zeolites can adsorb large quantities of adsorbate depending on adsorbate
size, aperture size, temperature and surface acidity of zeolites.

Zeolites have aperture or pore diameter of the order of molecular dimension therefore
molecules having diameter of the same order or larger than pore diameter or aperture are
excluded from entering the pores or super cages. Since larger molecules are excluded,
preferential adsorption and reaction can be done using zeolites. For examples separation
of O2 and N2 in air can be done using and 13 X-NaX zeolites.
a. Acidity :
The OH bridging a framework of silicon to a framework of aluminum acts as the
Bronsted acid site. Coordinately unsaturated Al sites give rise to Lewis acidity. Acidity in
zeolites increases with decreasing Si: Al ratios because acid sites are associated with Al
ions. Bronsted and Lewis acid sites play important roles in various catalytic reactions
involving hydrocarbons. Zeolites are used in catalytic cracking reaction in petroleum
industry.
b. Thermal stability :
0
Most of the zeolites are stable upto 400 C. Stability increases with increasing silica
content. Introduction of rare earth cations in zeolites result in stability upto 800 0C
c. Shape selectivity
Unique pore structure of zeolites results in its high shape selective properties. Shape
selectivity results due to:
– geometric restrictions on the access of reactants to the zeolite framework
– geometric restrictions on diffusion of reactants in or diffusion of products out from

catalysts
i. Reactant selectivity : Selective admission of reactants to zeolite pores due to pore size
restrictions is known as reactant selectivity. For example in case of cracking
reactions, n-heptane undergoes preferential cracking (relative rate 1) over
dimethylhexane (relative rate 0.09). The dimethylhexane, due to presence of branched
carbons, is unable to enter the zeolite pores.

ii. Product selectivity : When there is possibility of formation of multiple products ,

selective formation of product can occur due to restriction on size or diffusion
rates of the larger molecule. For examples when alkylation of methylbenzene is
carried out over pentasil zeolites all isomers p-xylne, m-xylene, and o-xylene are
probable products. However, due to pore diameter restrictions in pentasil zeolites
there is preferential production of p-xylene over ortho and meta forms as shown
in the figure below.
CH3OH +
iii. Molecular traffic control : This concept involves preferential diffusion of

reactants through one channel and diffusion of products out of another
interconnecting channel of a zeolite. Counter diffusion is minimized and product
selectivity is maximized by this process.

Characterization of zeolites
The physicochemical properties of zeolites are studied by various characterization

techniques such as XRD, FTIR, SEM etc. Fig. 2 gives the XRD profile of zeolites Y. The
presence of sharp peaks indicates high crystalline nature of zeolites. The peaks
correspond to different crystal planes in zeolites as shown in Fig 2. The Fig. 3 shows the
SEM image of zeolite Y. The surface acidity of zeolites can be measured using pyridine
probe in FTIR analysis or NH3-TPD.
900
800
(111)
(533)
700
(331)
(642)
600
(555)
Intensity
(440)
500
400
(511)
(840)
(311)
(822)
300
(220)
(664)
200
100
0
10 20 30 40 50 60 70 80
2θ in degree
Fig 2. Typical XRD profile of Zeolite Y
Fig .3. SEM image of zeolite Y.

Applications of zeolites
The principal applications of zeolites are discussed below.
i. Catalysts and catalyst supports

Acidity and shape –selective properties of zeolites play major roles in their use as
catalysts to produce premium quality fuels and chemicals. Zeolites because of
their acidity find applications in catalytic cracking, isomerization, alkylation and
aromatization reactions. Fluidized catalytic cracking is the largest and oldest
application of zeolite catalysts. Medium pore zeolites are being widely used in
conversion of light hydrocarbons to monocyclic aromatics, because of their ability
to selectively perform these reactions, while minimizing coke formation. For
same reactions, when small pore zeolites are used, no aromatics are produced and
severe operating conditions are required, whereas large pore zeolites produce
heavy aromatics and deactivate rapidly. The major advantage of large pore
molecular sieves, developed recently, is their ability to crack larger molecules,
such as present in heavy petroleum residue, more efficiently. Major commercial
catalytic processes using zeolites are summarized in Table 1.
Table 1. Commercial catalytic processes using zeolite catalysts
Zeolites Process Products

Faujasite Catalytic cracking
Gasoline, fuel oil
Faujasite Hydrocracking Kerosene, jet fuel, benzene, toluene,
xylene
Mordenite Hydroisomerization i-hexane, heptane
ZSM -5 Benzene alkylation Styrene
ZSM -5 Xylene p-xylene
isomerization
In addition to the well established commercial processes some other new

applications of zeolites are being developed. Conversion of n-hexane and n-
heptane to benzene and toluene is carried out on a PtBa/Zeolite L catalyst while,
isomerization of C5/C6 is done with Pt/mordenite /alumina catalyst. For ZSM-5
catalysts various applications are developed. For example, alkylation of benzene
and toluene to form high octane alkyl aromatics, methanol to gasoline, methanol

to alkene, toluene disproportionation to p-xylene, or selective catalytic reduction

of NO has been reported with ZSM-5 or modified ZSM- 5 catalysts.
ii. Selective adsorbents and drying agents

Zeolites have unique ability to adsorb water while rejecting larger molecules. For
many applications they are the best available drying agents. Used in drying air,
natural gas, organic solvents and refrigerants.
iii. Separation and purification of gasses and liquids

Zeolites are used in purification of gases and hydrocarbon liquids. The 5A (CaA)
and 13X(NaX) zeolites have been the most commonly used sorbents for air
separation. The typical commercial 5A used for air separation is made by
exchanging ~70% of the Na+ in NaA by Ca2+ ions. The nitrogen is preferentially
adsorbed on the zeolite.
iv. Various types of zeolites such as Zeolites A,X, ZSM-5, mordenite etc. are used
for removing H2O, NH3, NO,NO2,SO2, CO2 and other impurities from gas stream.
In gas cleaning, zeolites are normally used for the removal of H2O, SO2 and CO2
from sour natural gas stream. Zeolite 4A are used for removal of CO2 from
submarines and spacecraft. The CaA (Ca ion exchanged zeolites A) is used to
adsorb H2S from sour gas. They are also used for selective removal of NH3
produced during gasification of coal and for removal of NH3, SO2, NOx and CO2
from air. Separation of close boiling point mixtures of alkylphenols, such as
mixture of p-cresol (201.8)/2,6-xylenol (203 0C) or m-cresol (202.8 0C)/2,6-
xylenol has been attempted using Na-X zeolites[3]. Effect of the cation on the
selectivity has also been investigated. The Na-X zeolite adsorbs p-cresol and m-
cresol selectively from their mixtures with 2,6-xylenol, while Ca-X and Ba-X
zeolites preferentially adsorb 2,6-xylenol. The selectivity seems to be decided by
the diffusion in the zeolite framework.
v. Water and waste water treatment :
In water and waste water treatment zeolites are used for various purposes, mainly
for water softening, ammonia removal and heavy metal removal. Zeolite is used
for exchange of hard ions [Ca+2] with soft ions [Na+, H+] for softening water in a

broad range of pH values. It is one of the oldest applications. This is particularly

important in detergent industry. Zeolites can also remove dyes from the washing
liquor by hetero-coagulation and adsorption. Another application of zeolites is
separation of ammonia from drinking or wastewater. Ammonia in the
environment originates from metabolic, agricultural and industrial processes and
from water disinfection with chloramine. The zeolites are very effective for
ammonia removal, due to their high selectivity for ammonium ion in the presence
of competing cations, such as K+, Ca2+ or Mg2+. Metals having density higher
than 5 g/cm3 are generally considered as heavy metals. Among the heavy metals
Cd, Cr, Cu, Ni, Zn, Pb and Hg are well known with their toxicity and considered
as environmentally hazardous. Zeolites have been widely explored for removal of
heavy metals from natural or industrial wastewater. The removal efficiency of
zeolites depends upon the type and amount of zeolite, contact time, pH,
temperature, initial metal concentration as well as on presence of competitive
ions.
Text reference
• H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic Processes,

Wiley, VCH, 2006
• J. Weitkamp and L. Puppe (ed.), Catalysis and zeolites: fundamentals and
applications, Springer Verlag, 1999
• J. Cejka, A. Corma and S. Zones (eds.), Zeolites and catalysis: synthesis, reactions
and applications – 2010, Wiley, 2010
Journal reference
1. T. Sano, Y. Kiyozumi, M. Kawamura, F. Mizukami, and H. Takaya,T. Mouri, W.

Inaoka, and Y. Toida, M. Watanabe and K. Toyoda, ZEOLITES, 11(1991) 842-845
2. J. Kenneth, Jr. Balkus, T. Kieu, Ly, Journal of Chemical Education, 68 (1991) 875-877
3. A. Raychoudhuri, V.G Gaikar, Separations Technology 5 (1995) 91-96

Lecture 37
Polymerization
Polymers are macromolecules obtained by bonding monomers which are small molecules
consisting of unit structure of polymer that are repeated. Polymers with desirable
properties of toughness, strength and elasticity have molecular weight in the range of 104
to 106 g/mol. Polymer can be classified in different ways :
1. Based on thermal behavior

a. Thermoplastic : These polymers soften on heating.
b. Thermoset : This class of polymers have rigid three dimensional structure
and are not softened on heating.
c. Elastomers : These polymers have low crystallinity and high flexibility.
2. Based on structure
a. Homochain polymer
These polymers are synthesized from single monomer such as alkene (propylene,
vinylchloride, styrene) or dienes (butadienes). Different stereochemical arrangements of
substitutional R group around the carbon chain as shown in Fig. 1 result in polymers with
variation in properties. In isotactic arrangement substitutional R group lies on the same
side of the carbon chain as shown in Fig.1. In syndiotactic form R group alternate on
either side of the carbon chain. When there is random arrangement of the substitutional R
group on carbon chain the arrangement is known as atactic. The stereoregularity of
polymer has significant effect on the properties of polymers. Isotactic and syndiotactic
are crystalline where as atactic polymer are amorphous. Polypropylene exists in these
forms. Isotactic polypropylene polymer is semicrystalline material while atactic
polypropylene has rubber like properties.

Isotactic
R H R H H H
R R
Syndiotactic
R H R H R
H R H
Atactic
R H R H R H
H R H R
Fig. 1 . Different stereochemical arrangements of homochain polymers
b. Copolymer
Copolymers are prepared from two or more type of polymers. Different types of
copolymers are obtained depending on the sequence of bonding of two different
homochain polymers say A and B as shown in Fig. 2. Random copolymers have lower
crystallinity and greater elasticity. In block polymer, blocks of one type of homopolymer
structure are attached to blocks of another type of homopolymer. As a result in block
polymer, desirable properties from each of the co-monomers are obtained. The styrene-
butadiene thermoplastic elastomer is an example of block polymer while the
acrylonitrile-butadiene-styrene (ABS ) impact polymer is an example of network
polymer.
Fig. 2. Different types of copolymers that can be obtained from two homopolymers A & B

Polymers can be produced by both heterogeneous and homogeneous catalytic processes

though most industrial catalysts are heterogeneous. Catalysts are essential for initiation
and/or control of the polymerization process. Polymerization processes are different from
the other conventional catalytic processes in the fact that the catalysts are rarely
recovered unchanged at the end of the reaction. The catalysts generally remain within the
products as the separation cost is too high. Typically more than one ton of polymer per
gram of catalyst is produced.
Polymerization can be done either by :
1. Step growth (condensation) reaction or

2. Chain growth (addition or insertion) reaction
Step growth reaction
The step growth reaction involves condensation reaction of two different functions A and
B, present on two different molecules. The linkage between the molecules is formed by
elimination of smaller molecules such as water, alcohol, HCl, CO2 and other molecules.
For example the polyester oligomer is formed by condensation reaction of an acid
function with an alcohol eliminating H2O molecule and can react further with either a
monomer or an oligomer. Condensation reactions are typically catalyzed by acid, base
and/or metal ions.
HO(CH 2 ) x C − OH + HO − (CH 2 ) x COOH → HO − (CH 2 ) X C − O − ( CH 2 ) x − COOH + H 2O
Polymers such as polyester , polyurethane or polyamides are formed by step growth

condensations. Polyester is formed from the reaction of a diacid with a dialocohol
catalyzed by toluene sulfonic acid or metal salts. Polyurethane is produced from
condensation of di-isocyanate and di-alcohol catalyzed by tertiary amines (1,4 –
diazabibicyclo(2,2,2) octane and metal salts while polyamides (nylons) are synthesized
by condensation of diamine and diacid.

Chain growth reaction
Chain growth polymerization involves reaction of unsaturated monomer compounds such

as vinylic, acrylic or dienic or strained heterocyclic monomers. Reaction is initiated by
formation of an active site on a monomer and is a slow process. It is followed by rapid
propagation by addition of monomers to active sites by opening of double bond or ring.
Then there is transfer of active site to macromolecular polymer to end its growth and
begin further growth of another. Finally, in the termination step destruction of active sites
occurs. The active sites for chain growth polymerization include unpaired electrons as in
free radical polymerization, anions having carbon –metal or alkoxide , cations such as
carbenium or oxonium ions and co-ordination bonds with transition metals in Ziegler –
Natta or metallocene catalysts.
Polymers produced via chain polymerization include polyethylene, polypropylene,

polystyrene, polyvinyl chloride, polyvinyl esters, acrylonitrile etc.
Polymerization catalysts
As the cost of separation of catalysts from the products is high, polymerization catalysts
are usually not recovered at the end of the process. Hence it is essential that catalysts
should be non-detrimental to the product quality. The catalysts should also have high
activity so that minimum amount of catalyst is needed for the process. This will
minimize the amount of catalyst retained within the products.
Commercial polymerization catalysts can be broadly classified as follows :
1. Oxygen containing initiators such as peroxides for free radical polymerization.

2. Speciality acids, bases, metal ion compounds and organometallic complexes for
step (condensation) polymerization.
3. Ziegler Natta, metallocene or supported metal oxide catalysts for coordinative and
stereo specific polymerization.

Sometime catalyst additives are used which improve chain transfer, production rate and
stereoselectivity in free radical and coordinative polymerization. For example ethyl
benzoate is used as additive to improve the catalyst stereo selectivity.
Ziegler – Natta catalysts
Ziegler – Natta catalysts are prepared from transition metal halides such as chloride or
iodide of Ti, V, Zr, Cr, W, Co and aluminum (Mg or Li) alkyl. The titanium catalysts are
prepared by the interaction of TiCl4 and alkyl aluminium compounds in hydrocarbon
solvent. Titanium supported on magnesium salts are also used. For production of
polyethylene, poly propylene and polydienes Ti-Al or Ti-Mg complexes are typically
used. The homogeneous vanadium based catalysts such as VOCl3, VCl4 or VO (OR)3
with aluminum alkyls such as RAlCl2 are used for production of polymers by
copolymerization. The Ziegler – Natta catalysts are capable of stereoregulation during
polymerization reaction and thereby increases selectivity of a particular product. For
example Ziegler – Natta catalyzed process is highly selective for linear polyethylene
production.
Metallocenes catalysts
Metallocenes are highly stereo specific catalysts having increasing applications. These
catalysts consist of transitions metal (Zr, Ti or Hf) sandwiched between cyclopentadienyl
rings to form a sterically hindered site. Typical structure is shown in Fig.3.
R2
R2
M = transition metal Zr, Ti, Hf ;
R1 A= optional bridging atom Si,C ;

X
A R1 = methyl group ;
M
R1 R2 = H, alkyl or other hydrocarbon groups;
X
R1 R2
Fig. 3. Structure of typical metallocenes catalysts

These catalysts have high activity as well as stereoselectivity. The catalyst can produce
either isotactic or syndiotactic polypropylene and are called single site catalyst. Polymers
produced by metallocene catalysts have narrow molecular weight distribution. The main
limitation of metallocene catalysts is their higher cost compared to conventional Ziegler –
Natta catalyst. But due to higher activity and gradually decreasing price scenario
metallocene based industrial polymerization process are rapidly growing.
Supported metal oxide catalyst
Most industrial polymerization catalysts are supported. Supported metal oxide catalysts
include Cr, Mo, Co or Ni supported on alumina, silica, zirconia and activated carbon.
They are used commercially for low pressure polymerization of alkene. The most active
catalysts are Cr/SiO2, Zr/Al2O3 and Ti/MgO. These catalysts are observed to be active for
ethylene polymerization but are less effective for propylene production because of low
stereoregularity.
Chromium catalysts are extensively used in production of high density polyethylene

HDPE. These catalysts are of two types; supported chromium oxide and organometallic
compounds such as bis(arene)Cr0. Chromium oxides are supported on silica, alumina or
titania. The supports affect the molecular weight distribution. Sometime mixed
composition of inorganic and organic catalysts are also used.
The supported catalysts are rapidly poisoned, fouled or encapsulated by the polymer
product. To maintain catalyst activity, the catalyst must constantly undergo fragmentation
to expose new active catalytic sites.
Text References
• H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic

Processes, Wiley, VCH, 2006
• Piet W.N.M. van Leeuwen, Homogeneous catalysis: Understanding the Art,
Springer, 2004
• George Odian, Principles of polymerization , Wiley India, 2008.

Lecture 38
Fragmentation of polymerization catalysts
Many industrial polymerization reactions are carried out with supported catalysts.
Typically porous silica, MgCl2 or certain polymers are used as supports. For supported
catalysts on initiation of polymerization, the active sites on the catalyst surface are
rapidly fouled due to encapsulation by the polymer product. However, the catalyst may
undergo fragmentation due to accumulation of polymers within the catalyst particles.
This fragmentation results in exposure of new active catalytic sites and maintains the
catalytic activity. The fragmentation process ensures access of the monomers to the
active catalyst sites. The fragmentation of catalyst particles are typically observed for
olefin polymerization reactions such as polyethylene and polypropylene productions with
Ziegler–Natta catalysts. Fragmentation of catalyst particles results in higher polymer
yield. Since recovery of the catalyst particles from polymer product is difficult and
expensive, fragmentation of catalyst makes the catalyst particles small enough so that
final product quality is not affected. In the final product, the size of the catalysts particles
are in the range of ~ 100 nm which are embedded in large polymer particles of 200 -
1000 µm diameter.

Fragmentation and polymer growth models
1. Core – shell model

According to this model, catalyst particles do not break up in the beginning of the
polymerization process. Initially, polymerization occurs on the surface of the particle
which acts as a core. Then, the polymer grows in the form of a shell around the core.
After formation of accumulated polymer shell, the monomer has to diffuse through the
polymer layer to reach the catalyst surface, where it reacts. The model is more applicable
for catalysts with low porosity for which monomer diffusion is limited
Fig. 4. Core – shell model for polymer growth
2. Multigrain model
For highly porous catalyst monomer diffusion is less limited and monomer can penetrate
into the pores of the catalyst more easily. Consequently polymer can grow throughout the
particle and result in immediate fragmentation of the catalyst particles (Fig. 5).
Fig 5. Growth of polymer within the pores of porous catalysts

After initial breaking of catalyst particles into small fragments (microparticles),

polymerization reaction occurs on surface of microparticles according to core–shell
model. These microparticles together form porous macroparticles. This is the most
accepted model for particle growth in olefin polymerization. Scheme of polyethylene
morphology development during gas phase polymerization is shown in Fig. 6.
Fig. 6. Scheme of development of polymer with catalysts fragmentation
Several researchers have studied fragmentation of Ziegler–Natta catalyst for olefin

polymerization. The fragmentation behavior of the emulsion-based Ziegler–Natta catalyst
for propylene polymerizations was observed to be faster and more uniform than that of
the MgCl2-supported and silica-supported catalysts of similar chemical composition [1-
2].
Liquid phase polymerization
Radical polymerizations can be carried out both by homogeneous and heterogeneous

process depending on whether the initial reaction mixture is homogeneous or
heterogeneous. Bulk polymerization and solution polymerization are homogeneous
processes while suspension and emulsion polymerization are heterogeneous processes.
By heterogeneous polymerization thermal and viscosity problems can be controlled more
efficiently.

1. Bulk polymerization
Bulk polymerization of pure liquid monomer is the simplest process and carried out by
using initiator in the absence of diluent or solvent. For this process reaction rate is high
due to high monomer concentration and result in high yield per volume of reactor.
Another advantage is that the relatively pure product is produced. However, control of
the bulk polymerization, exothermic in nature, is difficult. The viscosity of the reaction
system increases rapidly even at relatively low conversion. The heat removal is difficult
due to high viscosity and low thermal conductivity of the polymer melt. Consequently
local hot spots may occur resulting in degradation and discoloration of the polymer
product. Bulk polymerization requires careful temperature control and strong elaborate
stirring equipment. Though, bulk polymerization is commercially less used,
polymerization of ethylene, styrene and methyl methcrylate are carried out by this
method. The heat dissipation and viscosity problem are reduced by carrying out
polymerization at low conversion. Bulk polymerization can be carried out in conventional
stirred tank reactor, long tubular reactor with high surface to volume ratio and screw
extruder reactors.
2. Solution polymerization
Solution polymerization of monomers is carried out with dissolved monomers and
initiators in solvent. Typical solvents include aromatic and aliphatic hydrocarbons,
esters, ethers, alcohol or water. The solvent acts as diluent and aids in transfer of the
heat of polymerization. In presence of solvent the stirring becomes easier since the
viscosity of the reaction mixture is decreased. Consequently controlling of process
temperature is much easier in solution polymerization compared to bulk polymerization.
However, in presence of solvent purity of the product is reduced particularly if there is a
difficulty in removal of solvent. Vinyl acetate, acrylonitrile and ester of acrylic acid are
polymerized in solution.

3. Suspension polymerization
Suspension polymerization is carried out by suspending relatively large droplets (10-
1000µm ) of insoluble monomers along with catalyst in water. The water to monomer
weight ratio varies from 1:1 to 4:1 in most polymerization. The monomer droplets are
prevented from coalescing by agitation and presence of stabilizers. The suspension
stabilizers are typically used in less than 0.1 wt% of the aqueous phase. Two types of
stabilizer are used :
1. Water soluble polymers such as poly vinyl alcohol, sodium poly styrene
sulfonate, hydroxypropyl cellulose etc.
2. Water insoluble inorganic compounds such as talc, barium sulfate, kaolin,
calcium phosphate etc.
Styrene , acrylic and methacrylic esters , vinyl chloride, vinyl acetate and tetrafluoro
ethylene are polymerized by suspension method.
4. Emulsion polymerization
Emulsion polymerization involves finely divided droplets of insoluble monomers
suspended in water. Hydrophobic monomer droplets, of diameter in the range of 0.5 -10
µm, are dispersed in water which also serves as heat transfer medium. In emulsion
polymerization water soluble initiators such as persurphates are used. The difference
between emulsion polymerization and suspension polymerization lies in the type and size
of the particles in which polymerization occurs and kind of initiator employed. Many
industrial polymers are produced by emulsion polymerization such as polybutadiene and
PVC.
Gas phase polymerization
Large scale production of polyethylene and polypropylene from gaseous monomer is

carried out using heterogeneous catalyst. Powdered catalysts are mixed with gaseous
monomers at the reactor entrance. Reactors are fluidized bed or stirred reactors. The
major advantage of this process is that monomers can be easily separated from polymers.
Catalyst residues are not separated from polymers.

Coordination polymerization
The polymerization catalyzed by transition metal complex such as Zieglar-Natta catalysts

or metallocene catalysts is also known as coordination polymerization. The Ziegler –
Natta catalysts system may be heterogeneous (some titanium based system) or soluble
(most vanadium containing species). The best known are derived from TiCl4 or TiCl3 and
aluminium trialkyl. These catalysts are highly stereospecific and can orient the monomer
in specific direction before addition to the chain. The Ziegler-Natta and metallocene
initiators are considered as coordination initiators that perform stereoselectivity by co-
ordination. The olefin polymerization is carried out in presence of Ziegler–Natta catalyst
(TiCl4 supported on MgCl2).
Mechanism and rate
Radical chain polymerization involves initiation, propagation, termination, chain transfer

and inhabitation. For free radical polymerization the mechanism of formation of polymer
using peroxide catalysts can be represented as follows:
Initiation : R − O − O − R → 2 R − O
*
i.
Addition : R + CH= CHX → R CH 2CHX  R '* ⇒ R − O*

'* ' *
ii. 2
iii. Propagation :
R 'CH 2CHX * + CH 2 = CHX → R ' ( CH 2CHX ) CH 2CHX *
R ' ( CH 2CHX ) CH 2CHX * + CH 2 = CHX → R ' ( CH 2CHX )2 CH 2CHX *
iv. Chain transfer: R1CH 2CHX * + R2CHXR3 → R1CH 2CH 2 X + R2CX * R3

v. Termination :
R1CH 2CHX * + R2CH 2CHX * → R1CH 2CH 2 X + R2CH =

CHX

Assuming that (a) overall rate of reaction is determined by rate of propagation and (b)
rate of initiation of free radical is equal to rate of their termination, the overall rate
equation can be derived as :
0.5
 f kinit 
roverall = k prop  0.5
 CM CI
 kterm 
CM = concentration of monomers
CI = concentration of initiators
k prop = rate constant for propagation
k init = rate constant for initiation
k term = rate constant for termination
f = 2 (for given mechanism) = ratio of initiators R'* formed by initiation reaction to that
consumed in subsequent addition reaction
The coordination polymerization on Ziegler–Natta catalyst is assumed to be initiated by

adsorption of monomer at an electron deficient surface vacant site on octahedral structure
of titanium metal alkyl complex. A transition complex is formed by opening of the
double bond. The complex is then rearranged by insertion of the monomer into the
growing chain. When the insertion occurs at the original chain growing site with respect
to metal ion and original vacant site is retained then the growth corresponds to isotactic
growth. However if the chain growth site and vacant site interchange, then the chain
growth corresponds to syndiotactic growth. The mechanism is shown in Fig. 7.

Cp
R'
Cl CH 2-CH 2 -R
Al
Ti
Cp Cl Cl
R' Cp
Cl R R'
Al R Cp
Cl
Ti Al
Cl Cl
Ti
-- -
CH
2
Isotactic
Cl Cl
CH
2
Cp
Cp Cp
CH2=CH2 R'
Cl
Al
Ti
Cl Cl CH 2-CH 2 -R
Vacant site
Cp
Syndiotactic
Fig. 7. Polymerization of ethylene with Ziegler-Natta catalysts
The Ziegler Natta catalysts are mostly heterogeneous in nature and adsorption processes
are most likely to occur during polymerization reactions. Various kinetic schemes have
been proposed assuming that polymerization centers are formed by the adsorption of
metal alkyl species on the surface of a crystalline transition metal halide and then chain
propagation occurs between the adsorbed metal alkyl and monomers. Langmuir
Hinshelwood rate law for adsorption and reaction on solid is frequently adopted for this
kind of reaction scheme. The rate expression for the heterogeneous Ziegler–Natta
catalyzed polymerization process can be derived by using following model.
Initiation 
C+A-R 
1
 C-A-R

2
C-A-R+M  M-C-A-R
M-C-A-R → C-A-M-R C= transition metal complex
A-R = metal alkyl

Propagation M-C-A-M x -R → C-A-M x+1 -R
M = monomer
Chain transfer M-C-A-M x -R → C-A-M-R+M x
Termination M-C-A-M x -R → C-A-M+M x R

Assuming the rate of initiation and termination to be equal and that the overall rate is
summation of rate of propagation and transfer, the overall rate can be derived as:
−
dC M
=
( 
)
k prop + ktransfer kinit  ( K 1C AR ) ( K 2C M ) 

 ( 1 + K 1C AR + K 2C M ) 
2
dt kterm
k init = rate constant for initiation CM = concentration of monomers

k prop = rate constant for propagation CA − R = concentration of metal alkyl
k transfer = rate constant for transfer K1 = equilibrium constant for step 1
k term = rate constant for termination K 2 = equilibrium constant for step 2
Industrial processes
Most polymerization processes are carried out in the liquid phase in batch reactor or
CSTR and only few are continuous. For continuous process plug flow or fluidized bed
with low residence time is used. Long residence time should be avoided in batch /CSTR
as it is associated with many disadvantages such as catalysts decay and accumulation,
polymer degradation, production of non-uniform polymer etc.
1. Polyethylene production (PE)

Different grades of polyethylene such as low density polyethylene (LDPE), high density
polyethylene (HDPE) or linear low density polyethylene (LLDPE) are produced
commercially.
Low density polyethylene (LDPE) and high density polyethylene (HDPE)
The LDPE or high pressure polyethylene is produced by radical polymerization. The

HDPE or low pressure polyethylene is synthesized by co-ordination polymerization.
Except LDPE, all other polymers of olefins are produced by co-ordination catalysts.
LDPE obtained by radical polymerization differs structurally from HDPE produced by
traditional Ziegler Natta co-ordination catalyst. The LDPE is more highly branched (both
short and long branch) than HDPE and is therefore lower in crystallinity and density. The
crystallinity of LDPE lies in the range of 40-60% and while that of HDPE in 70-90% .
The density of LDPE and HDPE lie in the range 0.91 -0.93 g/cm3 and 0.94-0.96 g/cm3

respectively. Compared to LDPE, HDPE has increased tensile strength, stiffness,

chemical resistance and upper used temperature. Most HDPE have number average
molecular weights in the range of 50000 -250,000 and have wide range of applications
such as bottles, housewares, toys, pails, film for grocery bags and food packing, pipe,
tubing, cables etc.
Linear low density polyethylene (LLDPE)
Co-ordination copolymerization of ethylene in presence of small amount of α-olefins

such as 1-butene, 1-hexene or 1-octene results in polyethylene that have structure,
properties and applications equivalent to the branched LDPE produced by radical
polymerization. This polyethylene is known as linear low density polyethylene (LLDPE)
and has controlled amount of ethyl, n-butyl and n-hexyl branches respectively.
The polyethylene can be produced by following methods :
i. LDPE is produced by free radical high pressure bulk polymerization process

ii. HDPE and LLDPE are produced by slurry-suspension process at moderately
low pressure. The process is carried out over supported catalysts such as
supported Cr or Cr organometallic or coordination catalysts such as
metallocene or Ziegler –Natta catalysts. The reaction conditions are 80- 150
0
C and 20-35 atm pressure. Supported catalyst is typically suspended in alkene
or cyclohexane solvent which also serve as the heat transfer medium. The
Ziegler–Natta(TiCl4/Al - alkyl/MgCl2 ) catalyst is more active than Cr based
catalysts.
iii. HDPE and LLDPE can also be produced by gas phase fluidized bed
polymerization over supported CrCO3 or Ti based catalysts.

2. Polypropylene production
Isotactic isomers of polypropylene are most useful. It is stronger and harder than
polyethylene and frequently used in block copolymer production. Various catalysts are
used for this process.
a. Using Zeigler – Natta catalyst : The process is carried out at 70 0C and ~13 atm
using slurry reactors. Catalyst are prepared by reducing TiCl4 with Al (C2H5)3 in a
cold hydrocarbon liquid to produce stereo-unselective form of TiCl3. On heating
to 100-200 0C, TiCl3 form convert to the stereo-selective form. Isotactic yield of
propylene is about 92 %. The final active catalysts contain TiCl3 and AlCl3.
0
b. Using MgCl2 supported TiCl3 catalyst : The process is carried out at 70 C and
13-20 atm pressure. It gives around ~ 95 % isotactic polypropylene yield. The
catalyst is prepared by first milling MgCl2 with ethy bezanoate extensively to
produce a highly active disordered state. Then it is treated with TiCl4 at 100 0C .
c. Metallocene catalysts are more active with higher stereo selectivity. 100 % yield
of isotactic or syndiotactic is possible.
Deactivation: CO, O2 and S compounds act as poison for the catalysts. Reactants are
passed through molecular sieve adsorbent column before treating with catalysts.
Text References
• H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic Processes,

Wiley, VCH, 2006
• Piet W.N.M. van Leeuwen, Homogeneous catalysis: Understanding the Art, Springer,
2004
• George Odian, Principles of polymerization , Wiley India, 2008.
Journal Reference
1. M. Abboud, P. Denifl, K.-H. Reichert, Macromol. Mater. Eng. 290 (2005) 1220.
2. H. L.Ronkko, T. Korpela, H. Knuuttila, T.T. Pakkanena, P. Denifl, T. Leinonen,
M. Kemell, M. Leskela, Journal of Molecular Catalysis A: Chemical 309 (2009)
40–49

Lecture 39
Carbon nanotubes (CNT)
Materials with nano sized channels such as carbon nanotubes have received significant
attention in recent years. In heterogeneous catalysis CNTs are being investigated as nano
reactors, supports, active components and adsorbents. Other applications include
electronic devices, gas and biosensors, nano-balance, scanning probe tips etc.
Carbon nanotubes were discovered in 1991 as minor byproduct during synthesis of

fullerene which is an allotrope of carbon, in which the atoms are arranged in closed
shells. Fullerenes consist of 20 hexagonal and 12 pentagonal rings as the basis of an
icosahedral symmetry closed cage structure. The structure is shown in Fig 1.
Carbon nanotube structures consist of graphene cylinders closed at either end with caps
containing pentagonal rings. C70 is smallest nanotube. Nanotubes are formed by rolling
up a graphene sheet into cylinder and capping each end with half of a fullerene molecule.
Different wrapping results in different structures (Fig. 1) and electronic properties.
Different wrapping
Fullerene Zigzag tubes
Chiral tubes
Armchair
tubes
Fig. 1 : Structures of fullerene and carbon nanotube

In zigzag tubes some of the C-C bonds lies parallel to tube axis and in armchair tubes few
C-C bonds lies perpendicular to tube axis. Chiral tubes have intermediate orientation.
Types of CNTs
Carbon nanotubes are of two types :
i. Single wall carbon nano tube (SWNT)

ii. Multiple wall carbon nano tube (MWNT)
Single wall nanotube (SWNT ) consist of one cylinder. It is made of single graphene
sheet rolled up into cylinder closed by two caps (semi fullerenes). The SWNTs have
diameter in the range of 0.5 -2.0 nm. The length is in the range of 50-150 μm length.
The SWNTs are microporous and the specific surface area is in the range of 1300 m2/g
(outer surface). SWCNTs are commonly arranged in bundles. SWNTs have less
topological defects and have better mechanical and electro physical properties. Electronic
properties of SWNTs are governed by two factors, tube diameters and helicity, which
further depend on the way graphene layer is rolled up, arm chair or chiral. Armchair
SWNTs shows conductivity as similar to metal whereas zigzag SWNTs behave as
semiconductors. In catalysis CNTs have high application as support. Electrical
conductivity, surface curvature and presence of inner cavity in CNTs make the metal –
support interaction different compared to that in activated carbon or graphite support.
Mechanically bent SWNTs present kink sites that are chemically more active. Metal
nanoparticles size depends strongly on metal-CNT interactions with stronger interaction
giving rise to smaller nanoparticles. Studies have shown that convex surface of CNTs are
more reactive than concave surface and the difference in reactivity increases when the
tube diameter decreases.
Multiwall (MWNT) nano tubes consist of many nested concentric SWNTs cylinders with
increasing successive radii. The concentric walls are spaced regularly at 0.34 nm similar
to inter graphene distance. MWNTs have outer diameter in range of 2 – 100 nm
depending on number of coaxial tubes present. MWNTs are usually mesoporous in nature
and specific area depends on the number of walls. The length of MWNTs can range from
few to hundreds μm. The advantage of MWNT over SWNT is that the multi-shell

structures of MWNTs are stiffer than single wall hence stability is higher. Also large
scale synthesis of MWNT is possible by various methods. The most common
characterization techniques of these materials are electron microscopy, Raman
spectroscopy, TGA , IR and UV-Vis.
Synthesis of CNT
There are two main methods for preparation of CNT
1. Sublimation of graphite with subsequent desublimation

This method involves condensation of carbon atoms generated from evaporation of
solid carbon sources of graphite. The sublimation of the solid can be done using
electric arc or laser ablation (Fig. 1) where the temperature reaches to 2500 -3500 0C.
Arc discharge Laser ablation
Fig. 2. Schematics for CNT formation by sublimation of graphite with subsequent desublimation.
The electric arc discharge method is one of the efficient techniques for synthesis of CNT.
Typically, about 60 to70 wt% of the arc-synthesized soot is CNT. The rest of the soot
comprises of fullerenes, amorphous carbon and catalyst nanoparticles. In electric arc
discharge production of CNT two graphite rods are used and a current is passed
continuously between the electrodes. The anode is drilled and filled with catalysts. The
metal oxides (Ni, Co, Fe) are used as catalyst. In some cases the catalyst/graphite
composite is used as electrode. The synthesis is performed in cooled chamber in presence
of helium, argon or methane environment. During the arcing, the catalyst/graphite anode

is evaporated and consumed with simultaneous carbon deposition around the cathode.
The quality of CNT samples depends upon arc stability, current density and cooling of
cathode. In laser ablation method the graphite target is subjected to laser and sublimated
carbon is recollected. Inert gas atmosphere is maintained within the chamber.
2. Decomposition of carbon containing compounds

The most used method to prepare CNT is pyrolysis of hydrocarbon gases or vapors such
as propane, butane, hexane, benzene, toluene etc. The method is also known as chemical
vapor deposition (CVD) process.
Chemical Vapor Deposition ( CVD )
By chemical vapor deposition CNTs can be produced in large quantities. The process
temperature can vary from 500 – 1300 0C. The hydrocarbon precursors include CH4,
C2H2, C6H6, alcohols etc.
550−1000 C 0
Hydrocarbon + Fe / Co / Ni catalysts → CNT
Fig. 3 . Schematics for carbon vapor deposition method
In CVD method there is initial dissociation of hydrocarbons followed by dissolution and

saturation of C atoms in metal nanoparticles. Thereafter there is precipitation of carbon.
Vapor-grown CNTs generally use metal catalyst particles. Fe, Co and Ni catalysts are
mostly used for the catalytic growth of CNT. More recently, CNTs have also been grown
from metal such as Au, Ag and Cu. Catalyst serves as nucleation sites and also promotes
pyrolysis of hydrocarbons.

Growth Mechanisms :
The growth mechanism of CNT on metal based catalysts and nonmetal based catalysts
are discussed below.
i. metal based catalysts

The growth mechanism of CNTs is yet to be fully established. In general it is proposed
that hydrocarbons adsorb on metal particles and are catalytically decomposed. This
results in carbon dissolving into particle. Upon supersaturation, carbon precipitates in
tubular crystalline form. However, various alternative models have been proposed and
appropriate description of growth depends on synthesis route and conditions used. Two
most described models are root growth and tip growth [1]. The growth mechanisms are
schematically explained in Fig. 4. For formation of CNTs the metal catalysts have to be
dispersed well on the substrate forming nano clusters on the substrate surface. When
there is a strong interaction between the catalyst clusters and substrate, the CNT grows by
the root-growth mechanism. The pyrolysis of hydrocarbons produces the carbon atoms
which are extremely mobile on metal surfaces and rapidly diffuse over and through the
metal particles. The graphite precipitates around the catalyst particles and cylindrical
structures are formed in a nested fashion from the catalyst particle, with the catalyst
particle at the root. The growth of the nanotubes stops when the catalyst particles are
completely covered with layers of carbon. The tip growth mechanism is observed when
the interaction between metal catalyst clusters and substrate is weak. Due to the weak
interaction, the catalyst particles are lifted off the substrate by the cylindrical structures
formed below it. While, the carbon nanotube base remains anchored to the substrate, the
tip carrying the catalyst particle grows toward the region of higher feed gas
concentration. The tip growth stops when the catalyst particle is covered with carbon
layers or when the supply of feed gas is cut off.

Root growth
Tip growth
Fig. 4. Schmatics showing root growth and tip growth mechanism of CNTs
Synthesis of carbon nanotubes over Fe catalyst on aluminium is described by

Emmenegger et al. [2] as follows. Initially the iron nitrate layer formed on the support
transforms to crystalline Fe2O3 film during heating under nitrogen. After acetylene is
introduced, Fe2O3 film is fragmented and smaller particles are formed. Fe2O3 crystals are
reduced to inter-mediate oxides such as Fe3O4, FeO by hydrogen released from pyrolysis
of acetylene. Finally metastable Fe3C is formed and growth of CNT occurs by tip growth
mechanism.
ii. Non-metal based catalysts (Ceramic and semiconductor catalysts)

Among non-metallic catalysts SiC is most widely used. The Fig.5 shows the carbon
nanostructure formation over silicon carbide by carbothermal reduction of silica. At first
stage SiO2 is reduced to SiC via a carbothermal reaction. In next step SiC nano particle
coalesce and finally carbon nanotube growth occurs on surface of SiC particles through
carbon precipitation and/or SiC decomposition. The carbon generation reaction is given
below.
SiC ( s ) + CO ( g ) 
→ SiO ( g ) + 2C ( s )

Fig. 5. Schematic representation of CNT formation over silica
MgO, Al2O3, zirconia, magnesium borates etc. are also reported to be used to grow
carbon nanotubes.
Characterization of CNT
X-ray diffraction pattern of CNTs are close to graphite. A graphite-like peak (002) is
present and measurements of interlayer spacing can be obtained from its position using
the Bragg law [3]. Carbon nanotubes are also active in Raman spectroscopy [3]. Most
characteristic features are : peak <200 cm−1 which is characteristic of SWNT, frequency
depend on tube diameter. The 1340 cm−1 is assigned to residual ill-organized graphite.
The 1500 - 1600 cm−1peak also characteristic of nanotubes. The TEM images are
essential for studying CNTs.
Application of CNT and CNT based catalysts
CNTs are used in several catalytic reactions as catalyst or catalyst supports. In particular
liquid phase reactions were studied extensively with MWNT. Higher surface area and
mesoporous nature resulted in significant decrease in mass transfer limitations compared
to activated carbon.
1. Hydrogenation reactions
This is one of the most studied catalytic reactions both in liquid and gaseous phases. Ni,
Rh, Ru supported on CNT were reported to be more active for hydrogenation reactions
compared to when supported on activated carbon. Hydrogenation reactions such as
hydrogenation of alkenes and α,β – unsaturated aldehyde have been reported for CNT
supported catalysts. Ruthenium nanoparticles supported on MWCNTs showed excellent
catalytic activity for hydrogenation of aromatic hydrocarbon. The 5wt% Pt/CNT catalyst

was reported to be significantly more active than 5wt% Pt/AC for hydrogenation of trans
–diphenylethene and trans β-methylstyrene [4]. Rhodium complex grafted on MWCNTs
was reported to be very active for cyclohexene hydrogenation [5] while Pd/CNT catalyst
was found to be active for benzene hydrogenation [6]. Pt supported on SWCNTs has
been found to be active and selective in hydrogenation of prenal (3-methyl-2-butenal) to
prenol (3-methyl-2-butenol) [7].
2. Reaction involving CO/H2

CNTs have been investigated for Fischer –Tropsch reactions, methanol and higher
alcohol synthesis and hydroformylation reactions. Copper promoted Fe/MWCNT catalyst
are active for Fischer-Tropsch synthesis with olefins [8]. Co-Re/Al2O3 deposited on
MWCNT by dip coating exhibited an enhancement in Fischer-Tropsch activity than
observed with a similar system without CNT arrays [9]. MWCNTs also have been used
as promoter for Cu-ZnO-Al2O3 catalysts for methanol synthesis using H2/CO/CO2 [10]
The complex [HRh(CO)(PPh3)3] has been grafted onto MCWNTs and used for
hydroformylation of propene. Higher conversion and higher regioselectivity toward n-
butaldehyde have been reported for CNT supported catalysts compared to that activated
carbon or carbon molecular sieve supported catalysts [11]
3. Ammonia synthesis and decomposition

The Ru/C catalyst is studied as an alternative to conventional iron based catalyst for
ammonia synthesis at high pressure and temperature. However, Ru/C catalyst is prone to
deactivation due to metal sintering, metal leaching or methanation of support. The
stability of the catalyst are reported to increase on using CNT as support. Ru-K/MWCNT
catalyst has been found to be significantly more active than Ru supported on other carbon
supports [12]. The catalytic decomposition of ammonia to generate CO- free hydrogen
for fuel cells is receiving increasing attention since the process is more economical than
using methanol as hydrogen source. The MWCNT supported ruthenium was found to be
more active than MgO, TiO2 or alumina supported Ru [13].

4. Polymerization
The CNTs have excellent thermal and electrical conductivities and reported to be used as
fillers in polymer based advanced composites. However due to poor solubility of CNTs,
homogeneous dispersion is difficult task. The polymer functionalized CNTs are prepared
following three approaches :
a. A non-covalent functionalization method in which polymers are produced by ring

opening metathesis polymerization. The coating of hyper branched polymers on
MWCNTs has been obtained via cationic ring opening polymerization of 3-ethyl-3-
(hydroxymethyl)oxetane with a BF3.Et2O catalyst [14]
b. A covalent functionalization performed by, first grafting polymerization initiators
onto the tubes through covalent bond and then exposing these CNT based macro-
initiators to the monomer. The polymer is obtained by atom transfer radical
polymerization. The polyethylene-MWCNT composite has been produced using
catalyst grafting procedure by polymerization of ethylene on [ZrCl2Cp2]
MAO/MWCNT where Cp= C5H5 and MAO = methylaluminoxane [15].
c. Olefin polymerization via anchored metallocenes catalysts. It has been proposed
that MWCNT play a key role in increasing the molecular mass. Supporting the
catalytic system on MWCNTs increases the polymerization rate of ethylene.
Syndiotactic polypropylene-MWCNT composites have been prepared by propylene
polymerization on zirconocene-MAO catalysts [16].
5. Fuel cell electrocatalysts

CNTs are used as catalysts supports for anode or cathode catalysis in direct methanol fuel
cells or proton exchange membrane fuel cells. The structure and properties of carbon
supports which constitute the electrode material have a direct impact on performance of
fuel cells. The most studied reaction s are methanol oxidation (anode catalyst), oxygen
reduction (cathode catalyst) and hydrogen oxidation (anode catalyst). The Pt is most used
metal followed by Pt-Ru system. The general observation is that CNT based catalysts are
more active and better resistant to poisoning compared to conventional carbon black
support. The advantage of CNT supports for fuel cell applications is attributed to :

a. Higher metal dispersion and higher electroactive surface area

b. Higher mesopores 3D network facilitating mass transport
c. Excellent conducting properties which improve electron transfer
6. Other applications
CNT is also being investigated as support for biocatalysts. CNTs have been used for
enzyme immobilization which increases enzyme stability, control of pore size, multiple
active sites and reduced mass transfer limitations.
CNTs have also been used as direct catalyst for some specific reactions such as
methanation to produce CO and CO2 free hydrogen , oxidative dehydrogenation of ethyl
benzene to styrene and oxidative dehydrogenation of propane to propene, selective
oxidation of H2S , oxidation of aniline, esterification and hydroxylations.
Book Reference
• B. Zoung, S. Han, R. Raja, G.A. Somorjai (Eds.) Nanotechnology in catalysis,

Vol 3, Springer Science 2007
• Yuri Gogotsi (Eds.) Nanotubes and nanofibres, Taylor & Francis, 2006
• M. H. Rümmeli, A. Bachmatiuk, F. Börrnert, F. Schäffel, I.Ibrahim, K.
Cendrowski, G. Simha-Martynkova, D.Plachá, E.Borowiak-Palen, G. Cuniberti
and Bernd Büchner
Nanoscale Research Letters 6 (2011) 303

Journal reference
1. I. Kunadian, R. Andrews, D. Qian, M. P. Mengu, Carbon 47 (2009) 384 –395

2. C. Emmenegger, J.-M. Bonard, P. Mauron , P. Sudan , A. Lepora, B. Grobety ,
A.Zuttel , L. Schlapbach, Carbon 41 (2003) 539–547
3. T. Belin and F. Epron, Materials Science and Engineering B 119 (2005) 105–118.
4. T.Onoe, S.Iwamoto, M.Inoue, Catal.Commun. 8(2007)701)
5. L.J. Lmus-Yegres, M.C. Román-Martinez de Lecea, Micropor. Mesopor. Mater.
109 (2008) 305
6. A.M. Zhang, J.L. Dong, Q.H. Xu, H.K. Rhee, X.L. Li, Catal. Today 93-95 (2004)
347
7. V. Lordi, N. Yao, J. Wei, Chem. Mater. 13 (2001)733
8. E.Van steen, F.F. Prinsloo, Catal. Today 71(2002)327 .
9. Y.H. Chin, J. Hu, C. Cao, Y. Gao, Y. Chang, Catal. Today 110 (2005) 47
10. X. Dong, H.B. Zhang, G.D. Lin, P. Chen, Y.Z. Yuan. K.R. Tsai, Catal. Lett. 85
(2003) 237
11. Y. Zhang, H.B. Zhang, G.D. Lin, P. Chen, Y.Z. Yuan. K.R. Tsai, Appl. Catal. A
187 (1999) 213
12. H.B. Chen, J.D. Lin, Y. Cai, X.Y. Wang, J. Yi, J. Wang, G. Wei, Y.Z. Lin, D.W.
Liao, Appl. Surf. Sci. 180(2001)328.
13. S.F. Yin, B.Q. Xu, X.P. Zhou, C.T. Au, Appl. Catal. A 277 (2004)1
14. Y. Xu, C. Gao, H. Kong, D. Yan, Y.Z. Jin, P.C.P. Watta, Macromolecules
37(2004)8846
15. D. Bonduel, M. Mainil, M. Alexandre, F. Monteverde, P. Dubois,
Chem.Commun.(2005) 781
16. K. Wiemann, W. Kaminsky, F.H. Gojny, K. Schulte, Macromol. Chem. Phys.
206(2005)1472

Lecture 40
Nano metal or metal oxide catalysts
Nano particles consisting of small metal or metal oxide crystallites in the range of few
nanometers (1-100 nm) are important for catalysis and adsorption. Nanoparticles have
higher effective surface area and improved physico-chemical properties giving better
performance. Uniform shape and sized catalysts are particularly important for structure
sensitive reactions where different type of surface metal atoms such as corners, edges or
terrace atoms possesses quite different properties.
Menezes et al. [1] studied the effect of particle size on catalytic activity of titania
supported Au-Ag (1:1) nanoparticles for CO oxidation. They observed that reactivity of
the catalysts increased as size of the nanometals decreased. They reported turn over
frequency of 0.02, 0.04 and 0.08 s-1 for nanoparticles having average size of 3,12 and 19
nm respectively.
Synthesis of nanoparticles
It is a challenge to prepare nanoparticles of uniform shape and size by conventional

methods. Various new preparation methods are reported that give nanoparticles with
narrow size distribution. Some of the reported methods are :
– Hydrothermal technique
– Microwave assisted synthesis
– Dendrimer assisted method
– Reverse micelle method
– Chemical vapor deposition

Hydrothermal method
In a hydrothermal process precursor solution, often in presence of an alkali, is autoclaved

at certain temperature for specific time. In a typical process, aqueous solution of
precursor and KOH is mixed and placed in teflon-lined stainless-steel autoclave.
Autoclave is maintained at 70- 200 0C for 10-24 h depending on process and then air-
cooled to room temperature. Resulting precipitate is collected by filtration, washed and
finally dried.
For example, nickel ferrite particles prepared by hydrothermal process resulted in

particles of size distribution from 40-90 nm as reported by Cheng et al. [2] .
NiCl 2 .6H 2O + Fe ( NO 3 ) 3 .9H 2O + KOH solution 

→ NiFe 2O 4
Microwave-irradiated synthesis
Microwave irradiated synthesis method is a new promising technique for the preparation
of size controlled metallic nanostructures. Xu et al. [3] reported preparation of Pt
nanoparticles supported on CNTs. In this method solutions of Pt precursor (H2PtCl6.
6H2O), ethylene glycol and KOH are mixed in vial and CNTs are uniformly dispersed in
mixed solution. Closed vial is then placed in microwave oven (2450 MHz, 800 W) and
heated for the required time. The resulting suspension filtered and dried at 120 0C. This
preparation method resulted in Pt nanoparticles on surface of CNTs having uniform
spherical shape with diameter of 15 ± 3 nm.
Dendrimer assisted synthesis
Dendrimer is highly ordered branched poly-amidoamine macromolecule with tree-like

topology and is used in preparation of nano-material. Dendrimer have multiple
coordination sites that are utilized to coordinate metal ions and synthesize metal clusters.
In this method metal ions in solution are complexed to dendrimer, mostly with amine
groups in the outer shell of OH-terminated poly-amidoamine. Complexed metal ions are
subsequently reduced to metal atoms which agglomerate into metal particle. Men et al.

[4] reported synthesis of dendritic polyphenylazomethines (DPA) dendron encapsulated

gold clusters having average cluster diameter of 2.2 nm.
M S : C8H17S
M
S S
S
S Aun SS M N
S S
S
M
:M
N
N S
SH
M N
N
N
Fig 1. Gold clusters with DPA dendron
Reverse micelle method
Reverse micelles are formed when surfactant molecules, possessing polar head group and
hydrophobic tail, are placed in non-polar solvent. In reverse micelle structure surfactant
molecules aggregate into nano sized spherical structures having core of polar head groups
and shell of hydrophobic tails. If small amount of polar solvent is present in the mixture,
it would be enclosed in core of reverse micelles. If this polar solvent contains an oxide
precursor then controlled hydrolysis of precursor will be achieved by mixing small
amount of water and small particles of metal oxide will form at core. Preparation of nano
Al2O3 by reverse micelle method is discussed below.
toluene toluene
R3NAl(OR)3
N N N N
N N N
H 2O AlOx N
N N N N
N N N N
Fig 2. Schematics showing formation of nano-sized particles of aluminium hydroxide by reverse micelle method.

A solution of inverse micelles is first formed by adding a long chain alkylamine to a

toluene solution. A small amount of water is trapped in the reverse micelle core. Mixing
the reverse micelle solution with an aluminium alkoxy amine adduct results in hydrolysis
of the aluminium alkoxide adduct and formation of nano-sized particles of aluminium
hydroxide after drying.
Reverse micelle synthesis method is also reported for preparation of supported metal
catalysts. Cheney et al. [5] reported synthesis of alumina supported Pt/Ni bimetallic
catalysts by reverse micelle synthesis method. In this method two microemulsions were
created by mixing 15% water, 10% surfactant and 75 % hydrocarbon( cyclohexane and
propanol). Ni and Pt precursors were added to microemulsion -1 and hydrazine to the
microemulsion -2. Each mixture was stirred separately for 1 h to allow micelles to
equilibrate. In microemulsion-1 reverse micelles were formed having aqueous core and
the Pt and Ni precursors were dissolved in aqueous polar core of the reverse micelles.
Thereafter, the microemulsion –2 containing the reducing agent was added to the
microemulsion -1 for insitu chemical reduction of the metals at reverse micelle core. The
alumina support was added to the solution and titrated with acetone to disrupt the
micelles and precipitate the nanoparticles onto the support. The supernatant was decanted
and the catalyst powder was rinsed with acetone. Residual surfactant was removed by
giving heat treatment in oxygen environment. By this method particles were obtained in
the range of 1.4-2.8 nm.

Application of nanocatalysts
1. Gold nanocatalysts
Supported gold nanoparticles have been reported to be very effective catalysts for
oxidation of alcohols. Gold supported on graphite can oxidize glycerol to
glycerate under relatively mild conditions. Under same conditions conventional
supported Pt or Pd oxidation catalysts are much less selective.
2. Sulfated zirconia nanocatalysts

These catalysts are highly effective in refining processes replacing liquid acid
catalysts. These are used in acid promoted catalytic reactions such as
alkylation,dehydration, isomerization etc.
3. Dendrimer encapsulated nanoparticles (DENs)

Pd-DENs catalysts are studied as carbon-carbon coupling catalysts. In Heck
coupling reaction, involving C-C coupling between aryl halides or vinyl halides
and activated alkenes in the presence of a base, the Pd-DEN catalysts show higher
activity and selectivity relative to other colloidal Pd catalysts.
4. Tungsten oxide and titanium oxide nanocatalysts

Tungsten oxide and titanium oxide due to their visible-ultraviolet band gap have
been extensively studied in electro-catalytic and photocatalytic applications.
5. Transition metal or metal oxide nanoparticles

Transition metal or metal oxide nanoparticles have found important application in
catalyzing growth of carbon nanotubes, carbon fibres, nanowires etc. Cobalt or
cobalt oxide nanoparticles mixed with Ni is used in synthesis of single walled
carbon nanotubes.

Text Reference
• B. Zoung, S. Han, R. Raja, G.A. Somorjai (Eds.), Nanotechnology in catalysis,

Vol 3, Springer Science 2007
• Yuri Gogotsi (Ed.) Nanotubes and nanofibres, Taylor & Francis, 2006
Journal reference
1. W.G. Menezes, V. Zielasek, K. Thiel, A. Hartwig, M. Bäumer, Journal of

Catalysis 299 (2013) 222–231
2. Y. Cheng , Y. Zheng , Y. Wang, F. Bao, Y. Qin, Journal of Solid State Chemistry
178 (2005) 2394–2397
3. H. Xu, L. Zeng, S. Xing, Y. Xian, L. Jin, Electrochemistry Communications 10
(2008) 551–554
4. Y. Men, M. Higuchi, K.Yamamoto, Science and Technology of Advanced
Materials 7 (2006) 139-144
5. B. A. Cheney, J. A. Lauterbach, J.G. Chen, Applied Catalysis A: General 394
(2011) 41–47

Lecture 41
Phase Transfer Catalysis
Phase transfer catalysis (PTC) refers to reaction between two substances, located in
different immiscible phases, in the presence of catalyst. Phase transfer catalysis is mainly
used for synthesis of organics such as pharmaceuticals, dyes, chemicals etc. In this
process one phase acts as a reservoir of reacting anions. The second phase, which is the
organic phase, contains the organic reactants and catalysts generating lipophilic cations.
The reacting anions enter the organic phase in ion pairs with lipophilic cations of the
catalyst. Since the phases are mutually immiscible the reaction does not proceed unless
the catalyst, usually a tetra alkyl ammonium salt, Q+X– is present. The catalyst transfers
reacting anions into the organic phase in form of lipophilic ion-pairs produced according
to the ion-exchange equilibrium (1a). In the organic phase the anions react such as in
nucleophilic substitution as shown in 1(b) where alkyl halides undergo nucleophilic
substitution. A variety of other reactions with participation of inorganic anions such as
addition, reduction, oxidation, etc. can take place efficiently using this methodology.
Na +Yaq− + Q + X org
−
 Na + X aq− + Q +Yorg
−
1(a)
Q +Yorg
−
→ R − Y + Q + X org
+ R − X  −
1(b)
The advantages of phase transfer catalysis can be summarized as :
• Elimination of organic solvents

• Elimination of dangerous, inconvenient and expensive reactants
• high reactivity and selectivity of the active species
• high yields and purity of products
• simplicity of the procedure
• low investment cost
• low energy consumption
• minimization of industrial wastes
• mild reaction conditions

Suitable catalysts for PTC are those having highly lipophilic cation (that is cation having
strong affinity for organics). The quaternary ammonium or phosphonium salts are most
extensively used as phase transfer catalyst.
Examples of phase transfer catalyst are as follows:
i. Tetra-alkyl-ammonium or phosphonium salts

• Tetra-n-butyl ammonium bromide
• Methyl-triethyl ammonium chloride
ii. Tri-ethyl-benzyl-ammonium chloride
Displacement reaction of 1-chloroctane with aqueous sodium cyanide is accelerated
many thousand-fold by the addition of hexa-decyltributyl-phosphonium bromide as
phase-transfer catalyst. Tremendous reactivity enhancement occurs due to generation of
quaternary phosphonium cyanide, which makes cyanide anion organic soluble and
sufficiently nucleophilic. In the absence of hexa-decyltributyl-phosphonium bromide
phase transfer catalyst, no reaction occurs.
Bu P + ( CH ) CH Br − [1]( 1.5 mol % )

C 8 H 17Cl 
3 2 15 3
NaCN , H O ,105 0C , 1.8 h
→ C 8 H 17CN ( 94% )
2
Mechanism
Mechanistic aspects of phase-transfer catalysis remain obscure, mainly due to difficulty

of investigating biphasic systems and the many complex parameters that must be
analyzed. Two pathways are proposed
i. Starks extraction mechanism

ii. Makosza interfacial mechanism

Starks extraction mechanism
According to this mechanism phase transfer catalyst moves back and forth across the
organic and aqueous phases. The onium salt (Q+X-) equilibrates with inorganic base
(MOH) in aqueous phase, and extracts hydroxide into organic phase. Onium hydroxide
(Q+OH-) then abstracts hydrogen from the acidic organic compound to give the reactive
intermediate Q+R¯.
Q+X- =tetra alkyl ammonium or phosphonium salts
MOH = inorganic base
Fig 1. Schematic diagram showing Starks extraction mechanism
Makosza interfacial mechanism
There is initial formation of metal carbanion at interface in the absence of phase transfer
catalyst. This is followed by extraction of metal carbanion species from the interface into
the organic phase by action of phase-transfer catalyst. The mechanism is more plausible
when phase-transfer catalysts are highly lipophilic and reluctant to enter aqueous phase.
Fig 2. Schematic diagram showing Makosza interfacial mechanism

Types of phase transfer catalysis
The phase transfer catalytic processes can be categorized as follows depending on the
number of phases involved.
i. liquid–liquid phase transfer catalysis

ii. solid–liquid phase transfer catalysis
iii. third-liquid phase-transfer catalysis
The liquid-liquid phase transfer catalysis has been discussed so far.
Solid – liquid PTC
Solid liquid PTC is used for conducting a wide variety of organic transformations. The
solid-liquid PTC usually involves reaction of an anionic reagent in a solid phase, with a
reactant located in contiguous liquid organic phase. In solid-liquid PTC, the first step
involves the transport of a reactant anion from the solid phase to the organic phase by a
phase-transfer cation. The second step involves the reaction of the transferred anion with
the reactant located in the organic phase. Solid – liquid PTC are used for alkylation of
highly acidic compound, preparation of amino acids or aldol-type condensation. The
process of hydroperoxide acylation in presence of anhydrous Na2CO3 using solid –
liquid PTC system can be demonstrated by a sequence of the following reactions as
suggested by Baj et al. [1] :
( ROOH )Org + ( Na2CO3 )S 

  ( ROO Na )i + ( NaHCO3 ) S

k − 1+
k −1
( ROO Na ) + ( Q Cl ) 
− +
i

+
 ( Q ROO ) + ( NaCl )
−
Org
k2
k−2
+ −
Org S
( Q ROO ) + ( R − CO − Cl ) → ( R − CO − OOR )

+ −
Org
'
Org
k3 '
Org
+ ( Q +Cl − )
Org
The scheme is shown in Fig 3. A hydroperoxy anion is generated at the surface of solid
Na2CO3 which form a highly lipophilic ion pair [ROO- Q+ ] with the catalyst cation. This
can be transferred deep into the organic phase where the specific reaction occurs
producing the product.

Fig 3. Schematic showing mechanism for acylation of hydroperoxides by acid chlorides in solid – liquid PTC
Third-liquid phase transfer catalysis
In 1984, Neumann and Sasson investigated the isomerization of allylanisole using

polyethylene glycol as catalyst in toluene and aqueous KOH solution and observed a
third-liquid phase formed between the aqueous and organic phases. Third liquid phase is
reported to be obtained at specified conditions :
i. For phenethyl bromide to styrene using tetra-butyl-ammonium-bromide (TBAB)

under phase-transfer conditions third-liquid phase only formed under conditions of
using TBAB and 40% of aqueous NaOH solution.
ii. Solvents of different polarities and the amount of NaOH are two important factors in
formation of third-liquid phase, the distribution of catalyst and the reaction rate

Advantages of third-liquid phase-transfer catalysis includes:
– higher reaction rates and selectivity

– easy separation of catalyst and product
– easy reuse and recovery of catalyst
Etherification reaction of aqueous sodium onitrophenoxide with 1-bromoctane can be
carried out under third-liquid phase-transfer catalytic conditions. The reaction scheme
shown in Fig 4 is proposed by Lin et al. [2].
Fig 4. Schematic showing mechanism for etherification reaction of aqueous sodium o-nitrophenoxide with 1-bromo-octane in
third-liquid phase transfer catalysis
Industrial processes:
Cyanation of alkyl chlorides
Cyanation of alkyl chlorides is a major way to produce nitriles. In the traditional process,
since R-Cl and NaCN are mutually immiscible, solvents (lower alcohols-water mixtures)
are used for reaction to proceed. In this process product has to be separated from the
solvent and the solvent is reused. Another disadvantage is that the wastes, produced in
substantial quantities, have to be destroyed and disposed.

In PTC methodology, neat alkyl chloride containing ~1% molar catalyst is stirred with
saturated solution of NaCN in water. Upon completion of reaction in organic phase,
which is often the pure product, is separated and product can be subsequently purified or
used as such. Aqueous phase, after separation of solid NaCl, can be reused by
introduction of fresh NaCN. Hence only waste in this method is solid NaCl.
RCl + NaCN 
→ RCN + NaCl
Text Reference :
• M. Makosza, Phase-transfer catalysis. A general green methodology in organic

synthesis, Pure Appl. Chem., 72 (2000) 1399–1403
• K. Maruoka (ed), Asymmetric Phase Transfer Catalysis, WILEY-VCH GmbH &
Co., 2008
• C.M.Starks, C.L.Liotta, M.Halpern, Phase transfer catalysis : Fundamentals,
Applications and Industrial Perspectives, Chapman & Hall, Inc. 1994
Journal reference
1. S. Baj, A. Chrobok, I. Gottwald, Applied Catalysis A: General 224 (2002) 89–95
2. P. Lin, H. Yang, Journal of Molecular Catalysis A: Chemical 235 (2005) 293–301

Lecture 42
Molecular modeling in heterogeneous catalysis
Heterogeneous catalytic cycles are complex process involving diffusion, adsorption,

surface reaction and desorption. Further catalytic reactions involves individual
phenomenon occurring on catalytic sites to overall reactions occurring in reactors which
can be up to the size of 1 m diameter. Hence reactions can range in wide length scales.
Relevant time scales can also span from femtoseconds (10-15 ) up to hours. This makes
modeling of catalytic reactions challenging. Heterogeneous catalysis is traditionally
considered as an experimental field and molecular modeling is emerging as
complementary to experimental studies. Different computational methods at different
time and length scales are co-linked to explain phenomenon from atomic to the
macroscopic level. Computer modeling can provide new insights into reaction pathways
and predict properties of catalysts. Modeling can be used to explain experimental results,
suggest new experiments and substitute experiments in the screening of different
catalysts or reaction conditions. Initially the modeling techniques need to be validated
against experimental studies.
Different levels of molecular modeling
Molecular modeling needs to be carried out at different levels using different

computational techniques. These models can then be correlated to obtain an overall view
from atomic to macroscopic level. The different methods of molecular modeling include :
1. Quantum chemical calculations

2. Atomistic simulations
3. Microkinetic modeling

1. Quantum chemical calculations

Quantum chemical calculation method provides information about the smallest details in
heterogeneous catalytic processes. Most detailed chemical informations are used to
predict the energies, electronic structures, spectroscopic properties of small arrangements
of atoms and catalytic chemistry. For example, activation energy barriers for individual
elementary steps on surfaces can be calculated which is difficult to predict by
experiments. Detailed information about presumed active sites for catalysis may be
obtained because the explicit chemical details of system are considered. The method is
based on solution of Schrödinger equation. Various methods have been advanced to solve
the Schrödinger equation such as semi-empirical methods and ab-initio techniques.
Semi-empirical methods
Semi-empirical methods are significantly less computationally demanding. This method

introduces approximations to facilitate evaluation of terms introduced by electron –
electron interactions. Method that has been most widely used for catalytic systems
containing transition metals is ZINDO (Zerner’s Intermediate Neglect of Differential
Overlap). This semi-empirical method is extensively used to describe the electronic
structure and the spectroscopic features of compounds [1]. It has also been used for
understanding the reaction mechanism. Ma et al. [2] reported molecular simulation of the
hydrodesulfurization mechanism of thiophenic compounds over molybdenum disulfide
using ZINDO.
Ab initio methods
These methods are more computational intensive. Among ab intio methods Hartree–
Fock (HF) method adequately represent electron correlation such as configuration
interaction and density functional theory (DFT). DFT calculations are reported more and
more for various catalytic systems. Fajin et al. [3] used DFT to study the effect of doping
of transition metals on gold catalyst for the reaction of oxygen dissociation. D’Amore et
al. [4] investigated the adsorption of TiCl4 on the surfaces of MgCl2 crystals by DFT
methods to study the structure of the active species in industrial MgCl2-supported
Ziegler–Natta catalyst used for ethene and propene polymerization.

2. Atomistic simulations
In addition to the events at the active site, physical adsorption and diffusion are important
steps in a full catalytic cycle as discussed earlier. These phenomena which occur on
longer time and length scales are analyzed using atomistic models. Atomistic simulations
are used to predict macroscopic thermodynamic and transport properties such as
adsorption isotherms, heats of sorption, diffusion coefficients and activation energies for
diffusion. The method use systems of hundreds or thousands of molecules. Molecular
simulation needs knowledge of the chemical composition and structure of the material.
Basic structures can be determined by X-ray diffraction studies or other techniques.
Simple potential functions describe the interaction energies between reactants and
catalysts. Dispersion, repulsion, electrostatic forces and intramolecular forces are
typically accounted. Induced dipole and other forces may also be included if they are
considered to be important. Methods include Montecarlo and Molecular dynamics
method.
3. Microkinetic modeling
Microkinetic modeling is used to link molecular-level informations about reactants,
products and reactive intermediates on heterogeneous surfaces obtained by atomistic
simulations and electronic structure calculations to macroscopic physical and chemical
phenomena in systems involving chemical transformations. It is done using model
parameters such as reaction rates, reactant conversion, product yields and selectivities
predicted by the previous levels.
In this method no rate-determining mechanistic step (RDS) is assumed in contrast to

more traditional models such as power law model or Langmuir– Hinshelwood–Hougen–
Watson model. The mechanism for the reaction system is predicted based on
experimental and theoretical study. All probable elementary steps are included. The rate
constant for each of the elementary steps are specified from experiment or theory and the
mechanism is then combined with the appropriate reactor design equations. The
equations are solved to obtain relative reaction rates, coverage of surface intermediates,
reactant conversion, product yields and selectivities. This is much more realistic method
than traditional models where assumption of RDS is required. Non requirement of initial

assumption of RDS in this method is more accurate as the RDS can change with reaction
conditions. However accurate parameters for all forward and reverse reactions are needed
to solve the equations of the model. Thus result in requirement of huge amount of
informations about interactions of chemical species with catalysts. This is one of the
major disadvantages of microkinetic modeling and resulted in limitation of its usage. At
present with simultaneous advances in spectroscopic, isotopic tracing and other
experimental methods, obtaining detailed informations has become more feasible and
consequently quantum chemical techniques and microkinetic models are being used more
frequently.

Quantum mechanics
Hartree-Fock, DFT method
Electronic structure and energies,

molecular structure
Atomistic simulation
(Monte carlo, Molecular dynamics method)
Molecular structure and energies
Thermodynamics properties
Transport coefficients
Reaction mechanism
Microkinetic modeling Rate constants
Reactor design equation
Overall reaction rates
Concentration profiles
Fig 1. Flow diagram showing different levels of catalytic modeling

Reference :
• Linda J. Broadbelt, Randall Q. Snurr, Applications of molecular modeling in

heterogeneous catalysis research, Applied Catalysis A: General 200 (2000) 23–46
• H. Höltje, W. Sippl, D. Rognan, G. Folkers, Molecular Modeling: Basic Principles
and Applications, Wiley-VCH , 2008
Journal reference
1. C. A.Wegermann, J. C. Rocha, S. M. Drechsel, F.S. Nunes, Dyes and Pigments

99(2013)839-849
2. X. Ma, H. H. Schobert, J. of Molecular Catalysis A: Chemical 160(2000)409–427
3. J. L.C. Fajin, M. Natalia, D.S. Cordeiro, J. R.B. Gomes, Applied Catalysis A:
General 458 (2013) 90– 102
4. M. D’Amore, R. Credendino, P.H.M. Budzelaar, M. Causa, V. Busico, J.of
Catalysis 286 (2012) 103–110

Zeolites: Composition and Structures

Uploaded by

Copyright:

Available Formats

Zeolites: Composition and Structures

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

Zeolites: Composition and Structures

Uploaded by

Copyright:

Available Formats

NPTEL – Chemical Engineering – Catalyst Science and Technology

Composition and structures

Fig 1. Schematic diagram of zeolites structures

Joint initiative of IITs and IISc – Funded by MHRD Page 1 of 56

Table 1. Compositions of common zeolites per unit cell

Zeolite type Na AlO2 SiO2 H2 O

Zeolite X 86 86 106 264

Zeolite Y 56 56 136 264

Zeolites are synthesized by crystallization from reactive forms of silicon, aluminum,

Joint initiative of IITs and IISc – Funded by MHRD Page 2 of 56

Preparation of ZSM-5 zeolite [1]

Preparation of NaX Zeolite [ 2]

a. High surface area and ordered pore structure

Joint initiative of IITs and IISc – Funded by MHRD Page 3 of 56

– geometric restrictions on the access of reactants to the zeolite framework

– geometric restrictions on diffusion of reactants in or diffusion of products out from

Joint initiative of IITs and IISc – Funded by MHRD Page 4 of 56

ii. Product selectivity : When there is possibility of formation of multiple products ,

iii. Molecular traffic control : This concept involves preferential diffusion of

Joint initiative of IITs and IISc – Funded by MHRD Page 5 of 56

The physicochemical properties of zeolites are studied by various characterization

Fig 2. Typical XRD profile of Zeolite Y

Fig .3. SEM image of zeolite Y.

Joint initiative of IITs and IISc – Funded by MHRD Page 6 of 56

The principal applications of zeolites are discussed below.

i. Catalysts and catalyst supports

Table 1. Commercial catalytic processes using zeolite catalysts

Zeolites Process Products

In addition to the well established commercial processes some other new

Joint initiative of IITs and IISc – Funded by MHRD Page 7 of 56

to alkene, toluene disproportionation to p-xylene, or selective catalytic reduction

ii. Selective adsorbents and drying agents

iii. Separation and purification of gasses and liquids

Joint initiative of IITs and IISc – Funded by MHRD Page 8 of 56

broad range of pH values. It is one of the oldest applications. This is particularly

• H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic Processes,

1. T. Sano, Y. Kiyozumi, M. Kawamura, F. Mizukami, and H. Takaya,T. Mouri, W.

3. A. Raychoudhuri, V.G Gaikar, Separations Technology 5 (1995) 91-96

Joint initiative of IITs and IISc – Funded by MHRD Page 9 of 56

1. Based on thermal behavior

Joint initiative of IITs and IISc – Funded by MHRD Page 10 of 56

Fig. 1 . Different stereochemical arrangements of homochain polymers

Joint initiative of IITs and IISc – Funded by MHRD Page 11 of 56

Polymers can be produced by both heterogeneous and homogeneous catalytic processes

Polymerization can be done either by :

1. Step growth (condensation) reaction or

Step growth reaction

HO(CH 2 ) x C − OH + HO − (CH 2 ) x COOH → HO − (CH 2 ) X C − O − ( CH 2 ) x − COOH + H 2O

Polymers such as polyester , polyurethane or polyamides are formed by step growth

Joint initiative of IITs and IISc – Funded by MHRD Page 12 of 56

Chain growth reaction

Chain growth polymerization involves reaction of unsaturated monomer compounds such

Polymers produced via chain polymerization include polyethylene, polypropylene,

Commercial polymerization catalysts can be broadly classified as follows :

1. Oxygen containing initiators such as peroxides for free radical polymerization.

Joint initiative of IITs and IISc – Funded by MHRD Page 13 of 56

Ziegler – Natta catalysts

R1 A= optional bridging atom Si,C ;

Joint initiative of IITs and IISc – Funded by MHRD Page 14 of 56