Unit IV - Surface Chemistry & Catalysis

Adsorbent is a substance that attracts other materials or particles to its surface. A substance that
adsorbs, that is, a solid substance endowed with the property of attaching other substances to its
surface without any covalent bonding, for example, activated charcoal.

Adsorbate is any substance that has undergone adsorption on the surface . a material that has
been or is capable of being adsorbed or accumulated on a surface of a solid.

Adsorption is a surface phenomenon which creates a film of the adsorbate on the surface of the
adsorbent. The word "adsorption" was coined in 1881 by German physicist Heinrich Kayser .
Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved solid to a
surface. Adsorption is a surface-based process while absorption involves the whole volume of
the material.

Absorption is a physical or chemical phenomenon or a process in which atoms, molecules or

ions enter some bulk phase – gas, liquid or solid material.

Physisorption and chemisorption

Physisorption Chemisorption

Physisorption occurs only at very low
temperatures falling below the boiling point
of the adsorbate.
Physisorption decreases with rise in
temperature
The heat evolved in physisorption is quite
low, varying generally between 4-40 KJ/mol.
Chemisorption can occur at all the
temperatures.
The magnitude of Chemisorption increases
with rise in temperature. This is just as the
magnitude of chemical reaction in a given
time increases with rise in temperature
Heat evolved in chemisorption is very high,
varying generally between 40-400 KJ/mol.

Reversible in nature Irreversible in nature

Favors multilayer adsorption Favors monolayer adsorption
Forces of attraction are Vander Wall’s forces Forces of attraction are chemical forces

It does not require any Ea It requires high Ea

It is not very specific It is very much specific

Freundlich adsorption isotherm explains the relation between amount of adsorbate undergone
adsorption compared to amount of adsorbate remain unadsorbed. An empirical relation between

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the concentrations of a solute on the surface of an adsorbent to the concentration of the solute in
the liquid with which it is in contact.

A graph between the amount (x/m) adsorbed by an

adsorbent and the equilibrium pressure of the adsorbate
at constant temperature is called adsorption isotherm
At low pressure graph is nearly a straight line.
x/m = kpn
x/m is the amount of gas adsorbed
k and n are constants
Here n is always less than one and therefore
x/m does not increase as rapidly as p
 At low temperature, the extent of adsorption increases rapidly with pressure.
 At low pressure, the extent of adsorption is found to be directly proportional to
the pressure.
 At high pressure (closer to the saturation vapour pressure of the gas), the
adsorption tends to achieve a limiting value.

Factors affecting adsorption

Surface Area: Increase in the surface area of the adsorbent, increases the total amount of gas
adsorbed. Example- finely divided metals (nickel, platinum) and porous substances (Charcoal,
silica gel) provides large surface area and are best solid adsorbents. Surface area of a powdered
solid adsorbent depends upon its particle size. Smaller the particle size, greater is its surface
area.

Effect of Temperature and Pressure: Adsorption is an exothermic process, according to Le-

Chatlier’s principle, the magnitude of adsorption should increase with decrease in temperature. it
is found to be true in case of physical adsorption because vanderwaal’s forces are strong at low
temperatures.

However, chemisorption first increases with rise in temperature and then decreases. The initial
increase shows that like chemical reactions, chemisorption also require activation energy.

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The magnitude of adsorption increases with increase in pressure as explained in Freundlich
adsorption isotherm.

Nature of the Gas More readly soluble and easily liquefiable gases such as NH3, HCl, Cl2 and
SO2 are adsorbed more effectively than permanent gases such as H2, N2, He and O2. The Van der
Walls or intermolecular forces which are involved in adsorption are more predominant in case of
easily liquefiable gas than permanent gas.

1. Explain Langmuir theory of adsorption? Write down the Assumptions involved during
the derivation of Langmuir adsorption isotherm?

In 1916, Irving Langmuir proposed an Adsorption Isotherm which explained the variation of
Adsorption with pressure. Langmuir Equation which depicted a relationship between the number
of active sites of the surface undergoing adsorption and pressure.

 Fixed number of vacant or adsorption sites are available on the surface of solid.
 All the vacant sites are of equal size and shape on the surface of adsorbent.
 Each site can hold maximum of one gaseous molecule and a constant amount of heat
energy is released during this process.
 Dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.
 Adsorption is monolayer or unilayer.

Where A (g) is unadsorbed gaseous molecule,

B(s) is unoccupied metal surface and AB is Adsorbed gaseous molecule.

Langmuir Adsorption Equation

Calculation of Equilibrium Constant

Langmuir proposed that dynamic equilibrium exists between

adsorbed gaseous molecules and the free gaseous molecules.
Using the equilibrium equation, equilibrium constant can be
calculated.

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Where Ka represents equilibrium constant for forward reaction

Kd represents equilibrium constant for backward direction.

According to Kinetic theory,

Rate of forward reaction = Ka [A] [B]

Rate of backward reaction = Kd [AB]

At equilibrium, Rate of forward reaction is equal to Rate of backward reaction

The above equation represents the equilibrium constant for distribution of adsorbate between the
surface and the gas phase.

Derivation: Langmuir Equation which depicts a relationship between the number of active sites
of the surface undergoing adsorption (i.e. extent of adsorption) and pressure.

N= Total number of sites available on the surface of adsorbent

θ = Fraction of surface sites occupied with gaseous molecules.

N (1– θ) = fraction of surface which are unoccupied by gaseous molecules.

Rate of forward reaction adsorption depends upon two factors: Number of sited available on the
surface of adsorbent, (1 – θ) and Pressure of unadsorbed gaseous molecule P A

Rate of forward reaction or Adsorption α N(1-θ)

Rate of forward reaction or Adsorption α PA

Rate of forward reaction or Adsorption = Ka PA N(1-θ)

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Similarly, Rate of backward reaction or Rate of Desorption depends upon number of sites
occupied by the gaseous molecules on the surface of adsorbent.

Rate of backward reaction or desorption α Nθ

Rate of backward reaction or desorption = Kd Nθ

At equilibrium, rate of adsorption is equal to rate of desorption.

Ka P N(1 – θ) = Kd Nθ

Where K =

K pA (1-θ) = θ

-1=

= +1=

= θ ……..This is known as Langmuir Adsorption Equation.

Assumptions of Langmuir Adsorption Isotherm

 The adsorbed gas behaves ideally in the vapor phase.

 Only a monolayer is formed by the adsorbed Gas.
 The surface of the solid is homogeneous so that each binding site has the same affinity
for the gas molecule.
 There is no lateral interaction between the adsorbed molecules.
 The adsorbed gas molecules are localized ie. They do not move around on the surface.

Drawbacks of Langmuir Adsorption Isotherm

 The first assumption holds at low pressure.

 The second assumption breaks down when the pressure of the gas is increased.
 Third assumption is not true because the actual surfaces are heterogeneous.
 Fourth and fifth assumptions are also not valid.

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Features of Langmuir Adsorption Isotherm

At low pressure KpA << 1, so that θ = K pA

The fraction of the surface covered is directly proportional to the Partial pressure of the gas
molecule. The behavior corresponds to First-order reaction and is depicted by the initial steep
rise of the Isotherm.

At high pressure, KpA ˃˃ 1, so the equation (e) reduces to θ = 1.

The entire surface gets covered by a monolayer of the gas there by making the reaction
independent of pressure. That is the reaction becomes zero order.

Since at low pressure, adsorption is proportional to pressure

At low pressure θ = K (pA)1

At high pressure θ = K (pA)0

At intermediate pressure, the following expression should hold good

θ = K (pA)n ( Freundlich Isotherm)

Since the adsorbed molecule has a low binding energy, it may easily shake off from the surface.
That is the molecule will remain on the surface for a very short time before it is desorbed. The
rate constant Follows Arrhenius-type relation
/
kdesorption = A
Hence 1/kdesorption is called the life time τ
τ = τ0

BET theory of Multilayer Adsorption

The concept of the theory is an extension of the Langmuir theory, which is a theory for
monolayer molecular adsorption, to multilayer adsorption with the following hypotheses:

1. Gas molecules physically adsorb on a solid in layers infinitely;

2. There is no interaction between each adsorption layer; and Langmuir theory can be
applied to each layer.
3. Molecule can be adsorbed in second, third…and nth layer, the surface area available for
the nth layer being equal to the coverage of (n-1)th layer.
4. The energy of adsorption in the first layer is E1, assumed to be constant and energy of
adsorption in succeeding layers is assumed to be the same as EL, the energy of
liquefaction of gases.

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 = + ( )
( )

vtotal = volume of the gas adsorbed,

vmono = volume adsorbed when the surface of the solid is covered completely with a monolayer
of the adsorbed gases
c is a constant depending upon the nature of the gas,
/
Where c = , E1 = heat of adsorption in the first layer and EL = heat of liquefaction of
the gas.
Adsorption Isotherms

Type I isotherms show a fairly rapid rise in the amount of

adsorption with increasing pressure up to a limiting value.
They are referred to as Langmuir-type isotherms and are
obtained when adsorption is restricted to a monolayer. Type I
isotherms have also been found for physical adsorption on
solids containing a very fine pore structure. If BET equation,
when P/P0<<1 and c>>1, then it leads to monolayer formation
and Type I Adsorption Isotherm is obtained.
Examples: Ammonia on charcoal at 273 K, nitrogen on
microporous carbon at 77 K).

Type II isotherms shows large deviation from Langmuir model

of adsorption.
The intermediate flat region in the isotherm corresponds
to monolayer formation.
In BET equation, value of C has to be very large in
comparison to 1.
Type II isotherm are frequently encountered, and represent
multilayer physical adsorption on non-porous solids. They are
often referred to as sigmoid isotherms.
For such solids, point B represents the formation of an adsorbed
monolayer.
(e.g. N2 (g) adsorbed at -1950C on Iron catalyst and N2
(g) adsorbed at -1950C on silica gel.

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Type III Adsorption Isotherm
 This Isotherm also shows large deviation from Langmuir model.
 In BET equation value if C <<< 1 Type III Adsorption Isotherm
obtained.
 This isotherm explains the formation of multilayer.
 There is no flattish portion in the curve which indicates that
monolayer formation is missing.
 level off near the saturation vapour pressure and are
considered to reflect capillary condensation in porous solids,
 the effective pore diameters usually being between 2 nm and 20 nm.
 The upper limit of adsorption is mainly governed by the total pore
volume.
 Examples Bromine (Br2) at 790C on silica gel or Iodine (I2) at
790C on silica gel. (e.g. benzene on iron(III) oxide gel at 320 K)
Type IV Adsorption Isotherm

 At lower pressure region of graph is quite similar to

Type II. This explains formation of monolayer
followed by multilayer.
 The saturation level reaches at a pressure below the
saturation vapor pressure .This can be explained on
the basis of a possibility of gases getting condensed
in the tiny capillary pores of adsorbent at pressure
below the saturation pressure (PS) of the gas.
 show no rapid initial uptake of gas, and occur when
the forces of adsorption in the first monolayer are
relatively small. These isotherms are rare.
 Examples bromine on silica gel at 352 K) and V (e.g. water vapour on charcoal at 373 K)
adsorption of Benzene on Iron Oxide (Fe2O3) at 500C and adsorption of Benzene on
silica gel at 500C.

Type V Adsorption Isotherm

 Explanation of Type V graph is similar to Type IV.

 Example of Type V Adsorption Isotherm is adsorption
of Water (vapors) at 1000C on charcoal.
 Type IV and V shows phenomenon of capillary
condensation of gas.

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Mercury Porosimeter

Mercury intrusion method is preferred for macropores materials with pore diameter greater than
50 nm. Maximum diameter that can be measured is usually 105 nm. Mercury intrusion method is
carried out in the instrument known as mercury porosimeter, Mercury is forced to enter the
poresof material under pressure, due to non-wetting nature of mercury, intrusion is met with
resistance. The pore radius ‘r' is related to the applied pressure

The wetting or contact θ angle between mercury and solid is on average lies in the range 130-
1400 and surface tension of mercury is 0.48 N/m2. p is in atm and r in nanometers.

 Smaller the pore radius higher is the pressure needed for mercury to intrude in the pore.
 At low pressure of (0-2) atm, mercury penetrates voids between particles.
 At moderate pressure range of (3-500) atm large macro pores are filled.
 At further higher pressure range of 500-2000 atm, smaller macro pores and large
mesopores are progressively filled.

In a typical mercury porosimeter data, volume of mercury penetrating into pores is plotted as a
function of applied pressures.

Intrusion of mercury into pores of various sizes. Here ‘r' represents the radius of pores. As
pore radius decreases in the order r1> r2> r3, required pressure for filling the pores increases
in order of Pressure 1< Pressure 2 < Pressure 3

BET Surface area analyzer

Working principle and instrumentation

The basic components of surface area analyzer given in the figure are

 Analysis chamber/manifold of accurately known volume and temperature

 Vacuum system with valve to manifold
 Source of adsorptive gas (typically, N2) with valve to manifold
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  Pressure transducer and temperature sensor
 Sample tube connected to analysis manifold
 Liquid nitrogen bath

Determination of internal surface area is based on adsorption and condensation of N2 at liquid N2

temperature, (77K). Initially, the sample is evacuated at 120-250°C followed by cooling to 77 K
by liquid N2. Then gradually the partial pressure of nitrogen above the sample is increased. Some
quantity of gas will be adsorbed by the sample and removed from the gas phase. After
stabilization the equilibrated pressure is recorded and amount of nitrogen adsorbed at each
equilibrated pressure is noted.

An adsorption isotherm is plotted; volume adsorbed as function of relative pressure p/po, is

plotted from the data. The pressure over the sample is gradually increased until pressure reaches
near saturation pressure, by when the complete adsorption isotherm is developed.

The desorption isotherm is measured by a step-wise reduction in pressure until a low pressure
over the sample is achieved. Although the volumes are adsorbed at different conditions, the
values are reported at STP conditions.

Homogeneous catalyst:
If the catalyst is present in the same phase as the reactants, it is called a homogeneous catalyst
and this type of catalyst is called homogeneous catalysis.

Heterogeneous catalyst:
If the catalyst is present in a different phase as the reactants, it is called a heterogeneous catalyst
and this type of catalyst is called heterogeneous catalysis.

Homogeneous Heterogeneous

Form Soluble metal complexes, Metals, usually supported, or metal oxides

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Phase Liquid Gas/solid
Active site well-defined, discrete molecules poorly defined
Temperature Low (<250°C) High (250 – 500°C)
Activity Moderate High
Selectivity High Low
Diffusion Facile Can be very important
Heat transfer Facile Can be problematic
Product separation Generally problematic Facile
Catalyst recycle Expensive Simple
Catalyst modification Easy Difficult
Reaction mechanisms Reasonably well understood Poorly understood

In acid catalysis and base catalysis a chemical reaction is catalyzed by an acid or a base. The acid
is the proton donor and the base is the proton acceptor, known as Bronsted-Lowry acid and base
respectively. Typical reactions catalyzed by proton transfer are esterifications and aldol
reactions.

Enzyme catalysis is the increase in the rate of a chemical reaction by the active site of a protein.
The Reacting groups are brought together in a proper orientation. The mechanism is similar to
chemical catalysis. By providing an alternative reaction route the enzyme reduces the energy
required to reach the highest energy transition state of the reaction. The reduction of activation
energy (Ea) increases the amount of reactant molecules that achieve a sufficient level of energy,
such that they reach the activation energy and form the product. like other catalysts, enzyme is
not consumed during the reaction (as a substrate is) but is recycled such that a single enzyme
performs many rounds of catalysis.

Precursors: reagents used as source of metals or functional groups for the preparation of
materials are known as precursors. A Compound that participates in chemical reaction to produce
another compound is known as precursor.

Doping: The action of adding a small amount of foreign atoms to form a solid solution in the
lattice of a non-metallic catalyst.

Loading : Addition of atoms mainly metals into the framework of crystalline catalytic materials
or adding metal into the matrix of amorphous catalytic material by a chemical process like
precipitation or co precipitation. Metal loading normally alters the structural and textural
characteristics of the catalytic material which favors desired chemical reaction.

Impregnation: Incorporation or Insertion of a foreign atom into a catalytic material is known as

impregnation

Calcination is a process of heating to high temperatures in air or oxygen., Calcination is also

used to mean a thermal treatment process in the absence or limited supply of air or oxygen
applied to ores and other solid materials to bring about a thermal decomposition.

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Ageing: Catalyst deactivation resulting from changes in structure or in texture of catalyst.
Changes of this kind are usually irreversible and the catalyst cannot be regenerated.

Regeneration: After undergoing a catalytic process surface sites and pores present on the
catalytic materials will get blocked, this can be regenerated by thermal process or chemical
process like thermal treatment or washing catalyst with reagents.

Sintering is the process of compacting and forming a solid mass of material by heat or pressure
without melting it to the point of liquefaction. Sintering reduces the surface area of the catalyst
and changes the surface structure. For a porous surface, the pores may collapse due to sintering,
Sintering is in general an irreversible process

Explain Micro porous, Meso porous and Macro porous materials with examples.

Based on the dimensionality of pores, solids are classified into following types: Microporous
materials, Mesoporous materials and Macroporous materials.

Microporous materials are those whose pore diameter is below 2 nm. Examples of the
materials included under this category are pure silica aluminosilicates (zeolites),
aluminophosphates. Mesoporous materials have pore diameter in the range of 2 – 50 nm.
Examples include silica based MCM type zeolites, carbon nanotubes. Macroporous materials
possess pore diameter above 50 nm. A few examples of the materials included under this
category are titania, silica and zirconia prepared from emulsion droplets as templates by sol-gel
method.

Catalyst preparation methods: process consists in the chemical transformation of a liquid (the
sol) into a gel state and with subsequent post-treatment and transition into solid oxide material.
Sol is a name of a colloidal solution made of solid particles few hundred nm in diameter,
suspended in a liquid phase. The gel can be considered as a solid macromolecule immersed in a
solvent.

The precursor for synthesizing these colloids consists of ions of metal alkoxides and
aloxysilanes. The most widely used are tetramethoxysilane (TMOS), and tetraethoxysilanes

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(TEOS) which form silica gels. Alkoxides are immiscible in water. They are organo metallic
precursors for silica, aluminum, titanium, zirconium and many others. Mutual solvent alcohol is
used. The sol gel process involves initially a homogeneous solution of one or more selected
alkoxides. These are organic precursors for silica, alumina, titania, zirconia, among others. A
catalyst is used to start reaction and control pH. Sol-gel formation occurs in four stages.

 Hydrolysis
 Condensation
 Growth of particles
 Agglomeration of particles

This technique can be used in ceramics processing and producing thin films of metal oxides.
Nano materials derived by this method have wide applications in electronics, medicine,
separation technology, and optics.

Advantages of Sol Gel method

 Preparation normally carried out at room temp.

 Chemical conditions are mild
 Gives better surface area
 Gives better pore sized particles
 Gives better nano scaled particles

Solution Combustion Synthesis

Solution combustion is a traditional method followed for the preparation of nanomaterials.

Solution Combustion synthesis (SCS) or self-propagating high-temperature synthesis (SHS).This
is an effective, ecofriendly and low-cost method for production of various industrially useful
nanomaterials. Commonly used fuels are mainly Ascorbic acid, glycine

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Oxidizer + Fuel oxide catalyst

Mix Stir Heat

Cool

Extract

Advantages of Solution Combustion method

 Nanoparticles of size 20-50 nm can be synthesized

 Time required for the reaction is very less compared to other methods
 Inert gas is not required for the reaction
 Less expensive
 Inert gas atmosphere is not required

Precipitation & Coprecipitation

In this process the desired component is precipitated from the solution. Co precipitation is used
for simultaneous precipitation of more than one component. Catalysts based on more than one
component/metal can be prepared easily by co-precipitation. The precipitation process is mainly
followed for preparation of bulk catalysts and support material such as Al2O3, SiO2, TiO2, ZrO2
etc.

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In general, the metal hydroxides are precipitated from their precursor salt solution because of
their low solubility. The precipitation of hydroxides can be performed either by starting from an
alkaline solution which is acidified or from acidic solution by raising the pH. However, most
hydroxides for technical application are precipitated from an acidic solution by the addition of an
alkaline precipitating agent. like ammonia or sodium bicarbonate. Highly soluble inorganic salts
such as nitrates, carbonates or chlorides are generally used as metal precursors. For example,
preparation of alumina is done by precipitating aluminium hydroxide from aluminium nitrate
solution by addition of ammonium hydroxide.

During precipitation, several processes occurs and the major steps are :

1. liquid mixing/supersatuartion
2. nucleation
3. crystal growth to form primary products
4. aggregation of the primary particles

Initial mixing or interdispersing of components in the solution has a significant effect on the
precipitation. Good mixing result in a more homogeneous product particularly in case of co-
precipitation. Rate of stirring primarily affects the nucleation whereas growth rate is much less
influenced by this factor. Stirring rate also affect the aggregation. Aggregate size can be
influenced by changing the stirring rate and the manner of mixing.

Top down and Bottom up approach

Synthesis of nanomaterial’s mainly classified into Top down and Bottom up approach. Bottom
up method start with atoms or molecules and build up to nanostructure facbrication is less
expensive. Top down method s- begin with a pattern generated on a larger scale then reduced to
nanoscale by nature cheap and quick to manufacture slow and not suitable for large scale
production.

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Supported catalysts are prepared by deposition of the active metal on the support materials. The
main purpose of using a support is to achieve an optimal dispersion of the catalytically active
component and to stabilize it against sintering. But in many reactions the support is not inert and
the overall process consists of two catalytic functions both for active components and support.
Supported catalysts are prepared in two main steps :

1. Deposition of the precursor of the active component on the support.

2. Transformation of this deposited precursors to catalytically active site.

The final active component can be in metallic state, oxide form or reduced from depending on
the requirements.

Unsupported catalysts : Metal oxides are usually solids. Their bulk character mainly depend on
the bonding character between metal and oxygen. Metal oxides have widely varying electronic
properties which include insulators (Al2O3, SiO2), Semiconductors (TiO2, ZnO, NiO), metallic
Conductors (TiO, NbO), superconductors. These are catalytically active substances where their
surface properties and chemistry being determined by structure and composition, bonding
character, coordination of surface atoms and hydroxyl groups incrystallographic phases. They
can develop acid base and redox properties. Acidic and basic sites and acid-base pair sites have
been identified on the surfaces of aluminas (Al2 O3) SiO2 is weakly acidic and MgO is basic
solid.

Metal-Organic Frameworks: MOF’s are highly porous, crystalline solids consisting of a three
dimensional network of metal ions attached to multidentate organic molecules. Similar to
Zeolites, the spatial organization of the structural units give rise to a system of channels and
cavities on the nanometer length scale. Due to their extremely high surface areas and their
tunable pore structure with respect to size, shape, and function, MOFs are highly interesting
materials for various applications. Eg: Catalytic reactions, Gas storage etc.

Hybrid catalysts combine the properties of Homogeneous and heterogeneous catalysis. The goal
of approach is to combine the positive aspects of Homogeneous catalysts in terms of activity,
selectivity and the variability of steric and electronic factors by the appropriate choice of ligands
with advantages of Heterogeneous catalysts such as ease of preparation and recovery of catalyst.
This can be achieved by immobilization of active metal complexes, Organometallic compounds,
enzymes on solid support. Eg: Anchoring of catalytically active species via covalent bonding on
the surface of inorganic supports such as SiO2, MCM-41, Zeolites etc.

Ship-in-a-Bottle catalysts Metal complexes which are physically entrapped in the confined
spaces of Zeolite cages are known as Ship-in-a-Bottle or tea-bag catalysts. The entrapped
complexes retain many of the solution properties. Here catalytic performance can be modified by
shape selectivity, electrostatic environment and acid-base properties of Zeolite host. These are
known as Host guest supramolecular compounds.

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Zeolites

It is an abbreviation for (Zeolite Scony Mobile Number 5) First synthesized by Mobil

Company in 1972. It replaces many Homogeneous Catalysts were used in many
petrochemical processes. ZSM-5 has two diameters for its pores : d1= 5.6 Å , d2= 5.4 Å
whereas, Zeolite Y has a diameter = 7.4 Å The ZSM-5 zeolite catalyst is used in the petroleum
industry for hydrocarbon interconversion.

ZSM-5 zeolite is a highly porous aluminosilicate with a high silica/alumina ratio.

 It has an intersecting two-dimensional pore structure.
 aluminum sites are very acidic.
 acidity of the zeolite is very high.
 reaction and catalysis chemistry of the ZSM-5 is due to this acidity.

Zeolites and related materials contain regular microporous, the diameter of which are determined
by structure of the molecule. The pore sizes are well defined and have dimensions similar to
those of small organic molecules. The geometric constraints may act on sorption of reactants, on
the transition state of the catalyzed reaction, or on the desorption of Products.

Activity and Selectivity of catalyst

Activity: The ability of a catalyst is to influence the rate of a particular reaction for the formation
of products.

Selectivity: The ability of a catalyst to direct a reaction to yield a particular product.

Based on that shape selective effects have been classified as

 Reactant shape selectivity

 Restricted transition state shape selectivity
 Product shape selectivity

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Reactant Shape Selectivity Cracking of n-heptane and 1-methylhexane – Kinetic diameter of n-
heptane is smaller than that of 1-methylhexane, so that the latteris not able to enter micropores so
that shape selective cracking of n-heptane takes place when both hydrocarbons are present in the
feed.

Transition state shape selectivity: Transalkylation of m-Xylene – The reaction is bimolecular

and formation of 1,3,4-trimethylbenzene has a less bulky transition state than the formation of
1,3,5-trymethylbenzene.

Product shape selectivity Alkylation of toluene – p-Xylene can be selectively formed by

methylation of toluene with methanol and zeolites whose pore openings only Allow p-Xylene to
be released. The o and m isomers either accumulate in zeolite cages or are isomerized to p-
Xylene.

Catalytic poisoning: Poisoning also known as chemical deactivation is due to chemisorption of

impurities on the active sites of the catalyst surface, thereby decreasing the number of active sites
available for catalytic reactions. This process can be reversible or irreversible. Compound of
sulphur and other materials are frequently chemisorbed on nickel, copper and Pt catalysts. In
reversible poisoning, the strength of adsorption bond is not great and activity is regained when
the poison is removed from the feed. When the adsorbed material is tightly held on the active
sites, poisoning is irreversible and permanent.

X-Ray Diffraction:

X-ray diffraction (XRD) is an characterization technique followed for determining the crystal
structure of materials. It detects crystalline materials having crystal domains greater than 3-5 nm.
It is used to characterize bulk crystal structure, particle size and chemical phase composition.

X-ray is a form of electromagnetic radiation have wavelength of from 0.01-0.7 nm. The spacings
between lattice planes in the crystal are comparable to Xrays. When an incident beam of X-rays
interacts with the target atom, X-ray photons are scattered in different directions. Scattering is
elastic when there is no change in energy between the incident photon and the scattered photon.
In inelastic scattering the scattered photon loses energy. These scattered waves may super
impose and when the waves are in phase then the interference is constructive and if out of phase
then destructive interference occurs. Atoms in crystal planes form a periodic array of coherent
scatterers. Diffraction from different planes of atoms produces a diffraction pattern, which
contains information about the atomic arrangement within the crystal.

The X-ray beams incident on a crystalline solid will be diffracted by the crystallographic planes.
Bragg's law for diffraction. It is given as sinθ=nλ/2d; where n = an integer λ = wave length of
the radiation d = spacing between two planes or layers θ = diffraction peak at a specific
angle.The spacing between diffracting planes of the atoms determinses the peak positions. The
peak intensity is determined by the atoms are in the diffracting plane.

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 Braggs analysis for X-ray diffraction by crystal planes

Phase Identification

The catalysts are generally composed of mixture of several phases. The diffraction pattern for
each phase is as unique as a fingerprint. Phases with the same chemical composition can have
drastically different diffraction patterns. Phase identification is based on the comparison of the
diffraction pattern of the specimen with that of pure reference phases or with a database.
Databases such as the Powder Diffraction File (PDF) and JCPDS contain lists for thousands of
crystalline phases. Various crystalline phases can be quantified based on the fact that each phase
of the mixture gives its characteristic diffractogram independently. The intensity of the peak
depends on the concentration of the species present in the mixture.

pXRD pattern of amorphous and crystalline materials

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Determination of Crystallite Size of a material by Scherrer equation

Diffraction from a crystal specimen produces a peak with a certain width. This is known as peak
broadening. The peak width depends on the size of the crystals. Peak width is inversely related to
crystal size; that is, peak width increases with decreasing crystal particle size.

D = Kλ / βcosθ

where K is a dimensionless constant,

2θ is the diffraction angle,
λ is the wavelength of the X-ray radiation, and
β = full width at half-maximum (FWHM) of the diffraction peak .

Crystallite size is inversely related to the FWHM of an individual peak. That is narrower the
peak, larger the particle size. Ultimately, the size of the nanomaterials purely depends on the
FWHM of the diffraction peak. Phase identification is another important task of XRD. In powder
X-ray diffraction, the phase corresponding to a particular plane can be identified by comparing it
with reference spectra from JCPDS.

Scanning Electron Microscopy

Microscope forms an enlarged image of the original object in order to convey its texture
morphology and internal structure. Two important terms of microscopy is

(a) Magnification = objective lens × eyepiece lens

(b) Resolution (rd) is defined as closest spacing of two points which can be clearly seen through
the microscope as separate entities.

SEM is most widely used type of electron microscope for study of microscopic structure. In an
electron microscope, a focused electron beam is used instead of light to examine objects, and to
obtain the image of the specimen on a very fine scale. Electrons are considered as radiation with
wavelength in the range 0.001 - 0.01 nm compared to 400- 700 nm wavelength of visible light
used in an optical microscope. The incident beam in SEM is also called electron probe. The large
number of lenses and electrons of very low wavelength, improves magnification and resolution
of electron microscopes. electron microscopes are extremely used to determine material
microstructure. Optical microscopes have a maximum magnification power of 1000, and
resolution of 0.2 μm compared to resolving power of the electron microscope that can reach
1,000,000 times and resolution of 0.2 nm.

Electron–Sample Interactions

The interaction of electron beam with samples results in secondary electrons and backscattered
electrons that are detected by standard SEM equipment.

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Secondary Electrons (SE): As incoming electrons pass through the specimen, they impart some
of their energies to electrons of nearby specimen atom. This causes ionization of the electrons of
the specimen atom and slight energy loss and path change of the incident electrons. These
ionized electrons then leaves the atom with a very small kinetic energy (5eV) and are termed as
secondary electrons. The secondary electrons escape from a volume near the specimen surface,
at a depth of 5–50 nm and hence are useful to gain topography related informations.

Backscattered Electrons(BSE) : Some of the electrons of the incident beam collides with the
specimen atoms that falls in the path and are reflected or back scattered. The production of
backscattered electrons varies directly with the specimen's atomic number of the specimen.
When backscattered electrons are detected, higher atomic number elements appear brighter than
lower atomic number elements. This interaction is utilized to differentiate parts of the specimen
that have different average atomic number.

Working principle and instrumentation

In SEM, there are several condenser lenses and one objective lens. Condenser lenses are for
electron probe formation, not for image formation. Two condenser lenses reduce the crossover
diameter of the electron beam. The objective lens further reduces the cross-section of the
electron beam and focuses the electron beam as probe on the specimen surface. Objective lens
thus functions like a condenser.

Fig. 3. Schematic diagram illustrating scanning electron microscope

Electron probe or beam is scanned across the specimen and the procedure is known as Raster
scanning. Raster scanning causes the beam to sequentially cover a rectangular area on the
specimen. The signal electrons emitted from the specimen are collected by the detector,
amplified and used to reconstruct the image according to one-to-one correlation between

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scanning points on the specimen and picture points on the screen of cathode ray tube (CRT).
CRT converts the electronic signals to a visual display.

Xray Photoelectron Spectroscopy

Xray Photoelectron Spectroscopy is also called ESCA that is electron spectroscopy for
chemical analysis. So in this particular technique we utilizing x-ray to excite a particular
material, then generate photoelectrons and eventually get a spectrum to finally, evolve with the
chemical analysis. It is also called electron spectroscopy, because electron which is emitted as
the photoelectron, that is being captured for the chemical analysis of a particular material. We
can analyze its elemental composition, chemical formula, empirical formula and chemical or
electronic state of the elements. So, we can easily determine the overall nature of a particular
element and its electronic state.

Features of XPS
Highly surface sensitive
Contamination on materials can be seen
Determination of elemental composition upto 10 nm
In solid-state physics, the work function (sometimes spelled workfunction) is the minimum
thermodynamic work (i.e. energy) needed to remove an electron from a solid to a point in the
vacuum immediately outside the solid surface. The electrons removed are of low energy and to
detect those electrons coming out without undergoing any collisions require ultrahigh vaccum.

A typical XPS spectrum is a plot of the number of electrons detected per unit time (Y-axis,
ordinate) versus the binding energy of the electrons detected (X-axis, abscissa). Each element
produces a characteristic set of XPS peaks at characteristic binding energy values that directly
identify each element that exists in or on the surface of the material being analyzed.

The number of detected electrons in each of the characteristic peaks is directly related to the
amount of element present in the sampling volume. To generate atomic percentage values, each
raw XPS signal must be corrected by dividing its signal intensity (number of electrons detected)
by a "relative sensitivity factor" (RSF), and normalized over all of the elements detected.

Signals detected from analytes at the surface much stronger than the signals detected from
analytes deeper below the sample surface. Thus, the signal measured by XPS is an exponentially
surface-weighted signal. If the BE of the electron is very high the overall Kinetic energy of the
electron will be very less.

Broad survey scan for 1–20 minutes measures the amount of all detectable elements,
High resolution scan for 1–15 minutes reveal chemical state differences (for a high signal/noise
ratio for count area result often requires multiple sweeps of the region of interest),
1–4 hours for a depth profile that measures 4–5 elements as a function of etched depth (this
process time can vary the most as many factors will play a role).
Spin Orbit splitting

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for unfavourable alignment Binding Energy is very less and for favourable alignment Binding
Energy is very high.

Auger Spectroscopy

X-rays and gamma rays are energetic enough to expel tightly held electrons from the inner
orbitals of the atom. The removal of an electron makes the electronic structure of the atom
unstable, and electrons in higher orbitals "fall" into the lower orbital to fill the hole left behind.
In falling, energy is released in the form of a photon, the energy of which is equal to the energy
difference of the two orbitals involved. Thus, the material emits radiation, which has energy
characteristic of the atoms present.

When a core electron is removed, leaving a vacancy, an electron from a higher energy level may
fall into the vacancy, resulting in a release of energy. Although most of the time this energy is
released in the form of an emitted photon, the energy can also be transferred to another electron,
which is ejected from the atom. This second ejected electron is called an Auger electron.

Satellites peaks arise when a core electron is removed by a photoionization. There is a sudden
change in the effective charge due to the loss of shielding electrons.

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Shake-up: The outgoing electron interacts with a valence electron and excites it (shakes it up) to
a higher energy level. As a consequence the energy core electron is reduced and a satellite
structure appears a few eV below (KE scale) the core level position.

Shake-off: The valence electron is ejected from the ion completely (to the continuum). Appears
as a broadening of the core level peak or contribute to the inelastic background.

Emission from non-monochromatic x-ray sources produces satellite peaks in XPS spectrum at
lower BE.

Ghost peaks are due to contamination of the x-ray source, which produces x-ray emission at
different wavelength and it can also due to contamination of the sample holder etc.

Department of Sciences & Humanities, Faculty of Engineering, Christ University, Bengaluru