A good heterogeneous catalyst is required to have high activity, selectivity, and stability.

1. Activity is measured as moles of product formed per unit time and mass of catalyst.

2.Selectivity is most generally defined as the amount of desired product divided by the total
amount of products, both desired and undesired, produced in a certain amount of time.

3. Catalyst stability describes a wide variety of properties, such as resistance to poisoning or

sintering, mechanical strength, and thermal stability, or the ability to be regenerated after
deactivation occurs (typically between 1 s and 5 years). All of these fundamental characteristics
are affected by the preparation technique and by the physical and chemical properties of the
chosen system.

Industrial large scale use of heterogeneous catalysts are summarized below:

***
CATALYST TERMINOLOGY - ATOM EFFICIENCY, E FACTORS AND
ENVIRONMENTAL FRIENDLINESS
The atom efficiency is the molecular weight of the desired product divided by the total
molecular weight of all products.
For example the conventional oxidation of a secondary alcohol
3C6H5CHOHCH3 + 2CrO3 + 3H2SO4 3C6H5COCH3 + Cr2(SO4)3 + 6H2O
has an atom efficiency of 360/860 = 42%. By contrast, the catalytic route
C6H5CHOHCH3 + 1/2O2 C6H5COCH3 + H2O
offers an atom efficiency of 120/138 = 87%, with water as the only byproduct.

Another indicator of environmental acceptability is the E factor the weight of waste or

undesirable byproduct divided by the weight of the desired product. The production of fine
chemicals and pharmaceuticals generate the highest amounts of waste per unit weight of product.
Atom efficiencies and E factors can be calculated from each other, but in practice E factors can
be higher due to yields being less than optimum and reagents that are used in excess. Also, loss
of solvents should be included, and perhaps even the energy consumption with the associated
generation of waste CO2.

To express that it is not just the amount of waste but rather its environmental impact, the
environmental quotient EQ as the E factor multiplied by an unfriendliness quotient, Q, which can
be assigned a value to indicate how undesirable a byproduct is. For example, Q = 0 for clean
water, 1 for a benign salt, NaCl, and 1001000 for toxic compounds. Evidently, catalytic routes
that avoid waste formation are highly desirable, and the more economic value that is placed on,
for example, the unfriendliness quotient, the higher the motivation to work on catalytic
alternatives.
***

SKELETAL CATALYST
Skeletal catalyst consists of two metals (an alloy) in roughly equal proportions, where one metal
is the desired catalytic material, and the other is dissolvable in hydroxide, is first made. This
alloy is crushed and leached in concentrated hydroxide solution. The soluble metal selectively
dissolves, leaving behind a highly porous sponge like structure of the desired catalytic metal.
Catalysts formed by this technique show high activity and selectivity, and have found wide use
in industry, particularly for hydrogenation and dehydrogenation reactions.

Advantages and Disadvantages of Skeletal Catalyst

The main advantages of skeletal catalysts are high activity at low temperatures, high selectivity,
and strength against attrition. Compared with precious metal catalysts, skeletal catalysts are
relatively cheap owing to high activity with base metals. Selectivity allows skeletal catalysts to
be employed in reactions on complex substrates such as pharmaceuticals. Selectivity also allows
high yields of intermediate products, such as methanol from syngas over skeletal copper, where
skeletal nickel would give methane.
Strength against attrition is particularly important for catalysts in slurry-bed reactors, where
physical breakage of the catalyst particles, ultimately to fines, can prevent their use for those
reactions. The strength of the high surface area skeletal structures can be contrasted against
activated carbon, which readily breaks down due to attrition in these types of environments. For
the few environments where attrition is still a problem (e.g., oxidative dehydrogenation of
alcohols), the skeletal catalytic material technique can find use in fuel cell electrodes or as
surface-catalyzed reactors.

The primary disadvantages of skeletal catalysts include deactivation and waste disposal.

CATALYST SPILLOVER in supported catalyst

The spillover of reactant is a well-known phenomenon in heterogeneous catalysis. It is due to the

diffusion of atomic or molecular intermediates, formed, e.g. by dissociation, from the catalyst to
the support material. The reverse spillover is the opposite process and it corresponds to the
diffusion of molecular species adsorbed on the support towards the catalysts particles
***
SUPPORTED CATALYST

Reason for using support materials is that in

many cases the active catalytic material, i.e.,
the precursor, is an expensive metal (e.g., Pt,
Pd, Rh, Au), which needs to be used sparingly.
This can be achieved by using supported
catalysts, where the active metal or the metal
oxide is dispersed on a porous solid support
with a high surface area with a predefined pore
structure and particle shape. Hence, the weight
fraction of the active catalyst can be low. The
support particle not only offers a high
surface area, but it also acts as a thermal
stabilizer, and it provides easy access of the Figure: Supported catalyst, consisting of small
reactive gas. It may also have bifunctional particles on a high surface area carrier such as silica
activity. The preparation of supported catalysts or alumina, along with two simplified model catalyst
clearly poses a significant challenge for the systems, which in general offer much better
manufacturing step; i.e., the challenge is how opportunities for characterization at the molecular
level.
to distribute a microscopic amount of metal
such that a large surface area is maintained, and a stable catalyst with high activity and
selectivity is obtained. The performance of supported catalysts critically depends on the
distribution of the metal within the porous support.

Depending on the environment under which the catalyst will operate, different types of solid
support materials are used. The most common supports in industry are solid oxide supports.
Typically, these materials include alumina (Al2O3), silica (SiO2), and titania (TiO2). Oxide
surfaces are generally covered with hydroxyl groups, which are usually represented as S-OH,
where S stands for aluminum, silica, or titanium. When contacted with water (during the
impregnation step), these groups can behave as Brnsted acids or bases by exchanging a proton
with the liquid solution, which gives them the ability to interact with several catalytic precursors.
However, under aggressive conditions, oxide supports may dissolve (high pH) or be chemically
attacked (low pH). Thus, as an alternative, carbon-supported catalysts, which are more stable
under these conditions, can be used. In addition, the use of carbon supports allows
straightforward recovery of the active metal, as the support can be easily burned off.

Silica (SiO2)
Silica is the support of choice for catalysts used in processes operated at relatively low
temperatures (below about 300 C), such as hydrogenations, polymerizations or some oxidations.
Its properties, such as pore size, particle size and surface area are easy to adjust to meet the
specific requirements of particular applications. Compared with alumina, silica possesses lower
thermal stability, and its propensity to form volatile hydroxides in steam at elevated temperatures
also limits its applicability as a support.
Most silica supports are made by one of two different preparation routes: solgel precipitation to
produce silica xerogels and flame hydrolysis to give so-called fumed silica. In the solgel route,
an alkaline (pH = 12) sodium silicate solution, called water glass, is mixed with sulfuric acid. At
low pH, the silicate ions convert into Si(OH)4 monomer units which polymerize to colloidal
silica particles and agglomerate into a hydrogel, a three-dimensional network of spheres. Sodium
and sulfate are removed by washing; Drying at moderate temperatures (150200 _C) produces a
so called silica xerogel, a highly porous network of interconnected silica spheres, which will
absorb water from the ambient atmosphere equivalent to 510% of its own weight. This xerogel
is insufficiently strong and lacks the macropores needed to prevent excessive pressure drops in a
reactor. Therefore the material is milled to powders with the desired particle size, and mixed
with binders and shaped into pellets or extrudates.

The pore structure is primarily determined by the size of the colloidal silica spheres and the way
in which these agglomerate in the hydrogel, but can still be subsequently affected by adding
acids or bases in the washing stage. The second preparation route uses flame hydrolysis, a
versatile way to produce all kinds of oxides with high specific surface areas. The advantages of
fumed silica over xerogels are the better mechanical properties and higher purity of the former.
The starting material to produce fumed silica is SiCl4, which is volatilized in air, mixed with
hydrogen and fed into a flame reactor, where the mixture reacts in a complicated scheme to give
an aerosol of nanometre-sized SiO2 particles and HCl. The latter is removed from the surface of
the silica by steam and air in a fluid bed. The thus-formed silica has a low density and needs to
be compacted before it is pelleted or extruded into larger shapes. The original size and
aggregation of the silica spheres can be controlled by several parameters such as the temperature
of the flame, the H2/O2 ratio and the SiCl4 content of the feed and the residence time in the
flame reactor.

Alumina
Owing to its excellent thermal and mechanical stability and its rich chemistry, alumina is the
most widely used support in catalysis. Although aluminium oxide exists in various structures,
only three phases are of interest, namely the nonporous, crystallographically ordered a-Al2O3,
and the porous amorphous g- and c-Al2O3. The latter is also used as a catalyst by itself, for
example in the production of elemental sulfur from H2S (the Claus process), the alkylation of
phenol or the dehydration of formic acid. Alumina supports are made by thermal dehydration of
Al(OH)3 (Gibbsite or Bayerite) or AlOOH (Boehmite).

Aluminium is found in nature in the form of bauxite (named after Les Baux, France), an ore
consisting of aluminium hydroxides, silica and other oxides. Depending on origin, the bauxite
contains mainly gibbsite (Surinam, Ural), boehmite (France) or diaspore (Balkan). Aluminium is
extracted from the ore by treating it with NaOH, yielding a Na2Al2O4 solution from which
Gibbsite is obtained by crystallization. As a consequence, Gibbsite always contains alkali, which
may be undesirable for some catalytic applications. Alkali-free aluminas are therefore prepared
by hydrolysis of aluminium alcoholate, e.g. Al(OC2H5)3, which yields a gelatinous form of
boehmite, also referred to as pseudo-boehmite. Yet another preparation route starts from
bayerite, formed by precipitation of Al(OH)3 from aluminium salts to which ammonia is added
in solution. Bayerite forms at high pH (about 12), boehmite at more neutral pH values. Alumina
exists in several forms, among which only the a-form is crystalline. The others, called
transitional aluminas, have spinel-like structures with different orders in which layers are
stacked. In the spinel structure of, for example, MgAl2O4, oxygen ions are packed in a fcc
manner, while Mg occupies tetrahedral and Al octahedral sites. As the stoichiometry of Al2O3
does not quite correspond to that of a true spinel, the transitional alumina structures are cation-
deficient and contain many defects. Nevertheless, the X-ray diffractograms are characteristic of
spinels. As a support, c-Al2O3 offers high surface areas (50300 m2 g1), mesopores of between
5 and 15 nm, pore volumes of about 0.6 cm3 g1, high thermal stability and the ability to be
shaped into mechanically stable extrudates and pellets. The thermal stability of c-Al2O3 can be
significantly improved by lanthanum oxide additives, which reduce the rate of sintering and
retard the conversion into other phases of alumina. Its surface contains several hydroxyls,
between 10 and 15 OH per nm2, the linear ones being Brnsted bases (H+ acceptors), and the
bridged ones Brnsted acids (H+ donor). After dehydroxylation, the surface develops Lewis
acidity (electron acceptor) on the uncoordinated Al+ sites. Whereas cristoballite presented a
realistic model for the surface of a silica support, such a convenient structure is not available
for the alumina surface. The hydroxyl population is varied, exhibiting linear as well as two- and
three-fold bridged species, which can be identified by vibrational spectroscopy. In solution,
alumina is a polyanion of positive charge at pH values below approximately 7 and negative at
higher values, offering many possibilities to bind many ionic catalyst precursors.

The highly stable a-Al2O3 is used in high temperature applications, such as in steam reforming,
or in cases where low surface areas are desired.

Carbon
Porous carbons are used as a support for noble metal catalysts in hydrogenation reactions of
organic compounds, particularly in liquid media. Active carbons, containing functional groups at
their surface, are usually prepared by the pyrolysis of wood, coal, coconut shells, etc. in an inert
gas, CO2 or steam at temperatures of between 800 and 1500C. Activation of the surface is
achieved by subsequent treatment in oxygen. Surface areas may be as high as 1500 m2 g1 with
micropores smaller than 1 nm. Treatment at higher temperatures leads to graphitic carbons of
low surface area. The advantages of carbon are relative chemical stability and the easy
recoverability of the expensive noble metals from spent catalysts. Carbon is the support of choice
for noble metals in low temperature hydrogenation catalysts, and also for liquid phase reactions.
Preparation of Supported Catalysts
There are in principle two ways to make supported catalysts:
(1) By coprecipitating the catalytically active component and the support to give a mixture that is
subsequently dried, calcined (heated in air), and reduced to yield a porous material with a high
surface area. This procedure is followed when materials are cheap and obtaining the optimum
catalytic activity per unit volume of catalyst is the main consideration.
(2) By loading pre-existing support materials in the form of shaped bodies with the catalytically
active phase by means of impregnation or precipitation from solution. This is the preferred
method when catalyst precursors are expensive and the aim is to deposit the catalytically active
phase in the form of nanometre-sized particles on the support. All noble metal catalysts are
manufactured in this way.
***
Active site determination
The term is often applied to those sites for adsorption which are the effective sites for a particular
heterogeneous catalytic reaction.
The overall chemical transformation in a catalytic reaction is known to depend on the nature of
the active site, its surroundings, and the path to access it. Therefore, the important properties of a
catalyst include an active site with the correct ensemble of metal atoms, metal ions, or other
active components such as oxides, a cavity around the active site that may change configuration
to facilitate binding of a specific reactant to the active site and expulsion of the product, and a
cavity wall that facilitates passage of the desired reactants and products from the ambient to the
active site.

Lewis concept of acid and base

Acid accepts pair of electrons and base donates a pair of electron
BF3 + NH3 ---> BF3-NH3
(acid) (base)
Bronsted concept of acid and base
Acid is able to donate proton and base has the ability to gain proton.

Determination of active sites:

1. Active site determination by Infrared spectra

The best identification of the potential active sites by IR spectroscopy is the direct detection of
their IR fingerprint. Eg., zeolites, for which the strong Brnsted-acid sites are often identified
through the (OH) band of hydroxyl groups. If this is not possible, specific methods must be
employed to obtain a spectroscopic response for the sites. The most common is the adsorption of
probe molecules, which provides IR spectra specific to the interaction with a single site.
The direct detection of adsorption sites by IR spectroscopy is often not possible, therefore
specific methods must be employed to obtain a spectroscopic response of the sites. The most
common is the adsorption of probe molecules which gives IR spectra specific to the interaction
with the site.
Selection of the appropriate probe molecule

The choice of the adapted probe will depend on many parameters: the chemical function
providing the interaction with the site under study; the size of the molecule, depending on the
site accessibility; the optimum of the interaction (sufficient to furnish valuable information, not
excessive so as to limit surface modifications); the spectral response, producing a signal intense
enough, with band positions sensitive to the interaction; stability on the surface catalyst to avoid
decomposition; and sufficient vapour pressure to be easily introduced in an IR cell.

The investigated sites are very often cations, acting as Lewis centres, but infrared spectroscopy
has also been widely used in order to characterize the metallic centres in oxides and deposited
metal complexes also.

Acidic sites . Basic probes (NH3, CO, NO, Pyridine)

Basic sites Acid probes (acetonitrile)

It is difficult to directly examine the nature of surface acid sites

Typically, probe molecules are used to evaluate the nature of surface sites The IR spectrum of
pyridine (a base) shows frequency shifts depending on whether it is interacting with a Bronsted
site or Lewis acid site

This can be used to distinguish a quantify the sites that are present on a catalyst surface.

2. Temperature-programmed desorption (TPD)

Temperature-programmed desorption by the dynamic method involves placing a sample in a

sample cell and pre-treating it to remove any adsorbed species from the active surface. Next, a
selected gas or vapor is chemisorbed onto the active sites until saturation is achieved, after which
the remaining adsorptive molecules are flushed out with an inert gas. Temperature (energy) is
increased at a controlled rate while a constant flow of inert gas is maintained over the sample.
The inert gas and any desorbed molecules are monitored by a thermal conductivity detector
(TCD). The TCD signal is proportional to the quantity of molecules desorbed as thermal energy,
monitored by a thermocouple, overcomes the binding energy. Quantities desorbed at specific
temperatures provide information about the number, strength and heterogeneity of the adsorption
sites. Analysis data are usually plotted as quantity desorbed versus temperature, or as both
temperature and quantity desorbed plotted over time. TPD setup is shown below:
Output Ex., is given in figure

TPD chromatogram of Hydrogen desorbing from alumina supported platinum. Three distinct
adsorption bond strengths are evident. The first peak is obtained at a temperature of 393 K. This
peak corresponds to the weak adsorption of hydrogen and may relate to desorption from the
support or from weak chemisorption. The second peak obtained at the next higher temperature
(493 K) probably corresponds to hydrogen spillover due to the presence of Pt on alumina. The
third and final peak obtained at 570 K corresponds to the hydrogen chemisorbed by Pt. This peak
is quantified to estimate the quantity of Pt available for catalytic activity in a reactor.

INFLEUNCE OF SIZE AND MORPHOLOGY ON CATALYTIC ACTIVITY

Morphology effects appear for reactions that are

structure sensitive. A good example is the reduction of
NO by CO on Pd, which shows the highest activity on
(111) planes and lower activity on open surfaces.
However, in the case of supported particles it is
difficult to control the particle shape independently of
particle size. However, by using a careful TEM
characterization it is possible to disentangle size and
morphology effects. An example is given by the NO
reduction of CO on Pd/MgO(100) model catalysts.
Figure shows the reaction probability as a function of Steady-state NO-reaction probability for
three different samples with different
temperature for three different samples having particle particle sizes.
sizes of 2.8, 6.9 and 15.6 nm. In the low-temperature
regime, the reaction is limited by the dissociation of NO, it can be seen that the largest particles
are the least reactive ones, while the smallest ones are less active than the middle sized ones. The
same evolution for the three different samples is also observed for the NO dissociation rate
measured on the same samples Here the shape of the particles play a vital role along with the
size. The largest particles have coalesced and present mainly (100) facets, which are the least
active for the reaction. The medium sized particles, which have a truncated octahedron shape that
mainly presents (111) facets, are the most active ones. Finally, the smallest particles, which
reveal also a majority of (111) facets, are a little less active because for that size (2.8 nm) the
proportion of edge sites is no longer negligible. These sites are, however, low-coordinated atoms,
which reveal low activity. The origin of the low activity on open surfaces (and low-coordinated
sites) emanates from the second type of adsorbed nitrogen atom, resulting from the dissociation
of NO, and which are strongly bound and thus do not desorb at the reaction temperature. In other
words, they poison the catalyst.

CATALYTIC DEACTIVATION, PROMOTERS & POISONING

If other gases than the reactants and products of the catalytic reaction are present and if these
foreign atoms are chemisorbed much more weakly than the intermediates of the catalytic
reaction, the presence of the foreign gas will be of no consequence for the kinetic of the catalytic
reaction. In this case the foreign gas behaves as an inert. If the foreign gas is chemisorbed much
more strongly than the intermediates, the surface will to a large extent become covered by
adsorbed foreign atoms. In this case the foreign gas behaves as a poison and the consequences
for the kinetics will mainly be a large decrease in the reaction rate.
The most complex situation occur when the binding energy for the foreign atoms is about equal
to the binding energy for the reaction intermediates. The coverage of foreign atoms on the
surface will then depend on the reaction conditions. The kinetics of the reaction under dynamic
poisoning may be quite complicated.
Catalysts lose their catalytic activity as a function of time. Some of them lose their activity in
minutes and some may last for up to ten years, but ultimately all catalysts undergo deactivation.
Causes of Deactivation:
Though mechanical, thermal and chemical factors contribute to deactivation, it is impossible to
separate and single out one reason. Temperature of operation influences the sensitivity to poison
as well as sintering. Both chemical and thermal forces can weaken a particle to cause mechanical
failure. The causes for deactivation are listed in Table 1.

Table 1. Causes for Catalyst Deactivation

Following processes primarily contribute to the loss of catalytic activity:
1 Sintering
The catalytic reaction takes place at the surface of the catalyst. For this reason the catalyst must
have a large area and the active component is present in the catalyst in the form of small
particles, which are much less stable than large particles. A catalyst will slowly loose catalytic
activity due to growth of the particle and loss of surface area.
2 Fouling
Catalytic activity may be lost due to the formation of carbon or due to the deposition of
impurities or of dust in the catalyst. The formation of carbon is in some cases reversible. The
catalyst can be taken of stream and the carbon removed by oxidation.
The reactant gas may contain impurities, a few examples are metalorganic compounds in
hydrodesulphurization or H2S in steam reforming. These impurities react with the catalyst and
reduces the catalysts activity. Fortunately, the reaction between catalyst and impurity is often
very strong and the impurity is completely absorbed in the first few percent of the catalyst bed.
The catalyst bed is then designed to be a little larger than initially necessary, and the catalyst
temperature is initially slightly lower than the nominal operating temperature. Over the lifetime
of the catalyst, the temperature of the catalyst is slowly increased to compensate for the loss of
catalytic activity due to fouling. Fouling by dust carried into the reactor can occur, a few
examples are removal of NOx from flue gases or removal of CO from exhaust from car exhaust.
In this case the catalyst must be manufactured in a shape, which will allow the dust to pass
through the reactor.
3. Dynamic poisoning
The more interesting situation occurs when the catalyst is partially and reversibly poisoned by
impurities in the reactant gas. The degree of loss of catalyst activity then depends on the
operating conditions.

Catalytic poisoning
Poisoning is a chemical effect, in which a poison (a chemical agent) reacts permanently with an
active site thereby deactivating the catalyst.

Solutions to the deactivation problem:

1. Harmful process conditions that can lead to deactivation which should be avoided or changed.
2. Decreasing the temperature of operation and increasing the reactive gas pressure can lower the
catalyst deactivation. For constant conversion, increasing the temperature gradually as the
catalyst activity decays.
3. Poisons in the feed stock should be avoided.
4. Optimization of support, in order to avoid catalyst sintering.
5. Addition of promoters to resist deactivation. For eg., addition of small amounts of SiO2. ZrO2
to Al2O3 stability (to enhance the support stability).
6. Addition of promoters to neutralize the effect of poisons, eg., Sulphur poisoning of Ni is
reduced in the presence of copper chromite, as Cu and Cr preferentially form sulphides.
***
 Application of Catalyst in Environment
The emission of carbon monoxide, nitrogen oxides (NOx), sulfur oxides (SOx), and all sorts of
organic compounds are responsible of environmental pollution. Catalysis has become
indispensable in converting these environmentally harmful molecules into more benign species
such as N2, H2O and CO2, although the latter is now a suspected greenhouse gas. Environmental
catalysts are now used in various applications,
e.g. large-scale processes such as cleaning flue gases from power plants, in the transport sector,
to catalysis in charcoal broilers in restaurants to decompose aromatic molecules formed during
grilling of steaks and hamburgers, in toilets to reduce unpleasant odors, to remove volatile
organic compounds (VOCs) in industry and to decompose ammonia in waste water streams.
1. Automotive Exhaust Catalysis
The exhaust consists of hydrocarbons, NOx, CO, H2 and O2. Unburnt gasoline and cracked
hydrocarbons such as ethylene and propylene are also substantial constituents of exhaust.
Gasoline contains additives such as benzene, toluene and branched hydrocarbons to achieve the
necessary octane numbers. The direct emission of these volatile compounds, e.g. at gas stations,
is a significant source of air pollution. Leaded fuels, containing antiknock additions such as
tetraethyl-lead, have been abandoned because lead poisons both human beings and the three-
way exhaust catalyst, especially for the removal of NO by rhodium.
The three-way catalyst, consisting of Pt and Rh particles supported on a ceramic monolith,
represents a remarkably successful piece of catalytic technology. It enables the removal of the
three pollutants CO, NO and hydrocarbons by the following overall reactions

Additionally, NO is reduced by H2 and by hydrocarbons. To enable the three reactions to

proceed simultaneously notice that the two first are oxidation reactions while the last is a
reduction the composition of the exhaust gas needs to be properly adjusted to an air-to-fuel
ratio of 14.7. At higher oxygen content, the CO oxidation reaction consumes too much CO and
hence NO conversion fails. If, however, the oxygen content is too low, the entire NO is
converted, but hydrocarbons and CO are not completely oxidized. An oxygen sensor is mounted
in front of the catalyst to ensure the proper balance of fuel and air via a microprocessor-
controlled injection system.

Catalytic converters used to convert the harmful exhaust gases to less toxic ones. The major
supporting structure is the monolith, covered by a 3050 mm layer of porous washcoat. The
latter is the actual support and consists largely of c-Al2O3 (7085%) and other oxides such as
ceriumoxide (1030%), lanthanumoxide or alkaline earth oxides (BaO). Some formulations use
NiO as a sulfur getter in the outer layers of the washcoat. Denser oxides such
as a-Al2O3 or ZrO2 are sometimes used as a diffusion barrier, to prevent incorporation of
rhodium in the support at high temperatures. Only 12% of the washcoats weight corresponds to
noble metals (Pt, Pd, Rh). Some manufacturers use all three, but most converters contain Rh
together with Pt. Recently, all-palladium converters have been also introduced.

Alumina, present in the gamma modification, is the most suitable high surface area support
for noble metals. The -Al2O3 in washcoats typically has a surface area of 150175 m2 g1.
However, at high temperatures -alumina transforms into the alpha phase, and stabilization to
prevent this is essential. Another concern is the diffusion of rhodium into alumina, which calls
for the application of diffusion barriers.
Ceria is a partially reducible oxide (its reduction is promoted by the noble metals). When the
air/fuel oscillation swings to the lean side it takes up its maximum capacity of oxygen; this
oxygen is available for CO2 formation when the composition swings to the rich side. Ceria thus
counteracts the effect of oscillating feed gas compositions. It further stabilizes the high surface
area of the -Al2O3 by inhibiting its phase change into the a-phase and it impedes the
agglomeration of the noble metals and the loss of noble metal surface area by acting as a
diffusion barrier. Oxygen vacancies, conceivably also in regions where CeOx is in contact with
noble metal, are active sites for CO oxidation by O2, or by H2O through the water-gas shift
reaction.
Lanthanum oxide is valence invariant, and does not exhibit any oxygen storage capacity, but it
effectively stabilizes -Al2O3. It spreads over the alumina surface and provides a barrier against
dissolution of rhodium in the support.
Platinum serves as the catalyst for the oxidation of CO and hydrocarbons. It is relatively
insensitive to contamination by lead or sulfur. At high temperatures it is not known to dissolve in
the washcoat, but sintering into larger particles may lead to a substantial loss of platinum surface
area with dramatic consequences for the overall oxidation activity.
Rhodium is the crucial ingredient of the three-way catalyst. The metal, a byproduct of Pt
extraction, although expensive, rhodium is difficult to replace owing to its unique properties with
respect to NO surface chemistry. Loss of rhodium activity is due to particle growth under
reducing conditions (>900 K), and to diffusion into the alumina support under oxidizing
conditions (>900 K). . Palladium can be present in addition to Rh and Pt but may also replace
them. Palladium is as good for oxidation as platinum (even for the oxidation of saturated
hydrocarbons) but it is somewhat less active for NO reduction. Hence, noble metal loadings of a
Pd-only catalyst are 510 times higher than for a Pt- Rh catalyst. Palladium is less resistant to
residual lead in gasoline than Pt. Palladium catalysts also require higher ceria loadings to help
prevent high-temperature deactivation.

The ideal operating temperatures for the three-way catalyst lie between 350 and 650 C. After a
cold start it takes at least a minute to reach this temperature, implying that most CO and
hydrocarbons emission takes place directly after the start. Temperatures above 800C should be
avoided to prevent sintering of the noble metals and dissolution of rhodium in the support.
IN SITU CHRACTERIZATION OF CATALYST

Techniques normally used:

1. Infrared Spectroscopy
2. LEED
3. Scanning Tunneling Microscopy and Atomic Force Microscopy
4. Raman Spectroscopy
In infrared spectroscopy a molecule absorbs photons with the same frequency as its vibrations. In
contrast, Raman spectroscopy is based on the inelastic scattering of photons, which lose energy
by exciting vibrations in the sample. Figure illustrates the scattering process. Monochromatic
light of frequency v, falls on a sample, where the majority of the photons undergo Rayleigh
scattering, i.e.scattering without energy exchange. In a quantum mechanical picture it is as if the
molecule is excited to an unstable state with energy hv0, above the ground state, from which it
decays back to the ground state. No energy is exchanged between the molecule and the photon.
When, however, the excited molecule decays to the first vibrational level with frequency vvib, it
effectively takes an amount of energy equal to h vvib, away from the photon. Hence the scattered
light exhibits intensity at the frequency v0- vvib. This
Raman peak is called the Stokes band.
The reverse process may also take place. If the
collision with a photon brings a vibrationally excited
molecule to the unstable state of energy hv0+hvvib, it
may decay to the ground state, transferring a net
amount of energy h v v i b to the photon, which
leaves the sample with a higher frequency equal to
v0+vvib. This peak, called the anti-Stokes band, has
much lower intensity than the Stokes band, because
the fraction of vibrationally excited molecules is
usually small.

A strong point of Raman spectroscopy for research

in catalysis is that the technique is highly suitable for
in situ studies. The spectra of adsorbed species Fig. The Raman effect
interfere weakly with signals from the gas phase, enabling studies under reaction conditions to be
performed. A second advantage is that typical supports such as silica and alumina are weak
Raman scatterers, with the consequence that adsorbed species can be measured at frequencies as
low as 50 cm-1. This makes Raman
spectroscopy a powerful tool to study
catalytically active phases on a support.
A disadvantage of the technique is the small
cross sections for Raman scattering; most of
the scattered intensity goes into the Rayleigh
band, which is typically about three orders of
magnitude stronger than the Stokes bands. Of
course, the use of an intense laser increases all
intensities, but this has the disadvantage that
the sample may heat up during measurement
and surface species may decompose or desorb.
Experimental set-up for in situ or dynamic
X-ray diffraction studies of catalysts
Finally, fluorescence of the sample, giving rise to spectral backgrounds, may seriously limit the
detectability of weak signals.

5. Transmission Electron Microscopy

6. Temperature programmed desorption
7. In situ XRD (for following solid state catalysis reactions)
Since X-rays have considerable penetrating power, such that XRD can be used to study catalysts
under in situ conditions. Figure shows a set-up for in situ XRD studies which consists of a cell
with windows which are largely transparent to X-rays and a heating stage covered by a platinum
foil, which serves as a thermally conducting sample holder for the powdered catalyst. This cell
was used for eg., to follow the reduction of alumina-supported iron oxide at 675 K as a function
of time.