HETEROGENEOUS CATALYSIS

Ph.D. Course Work Report Submitted by

POONAM REDDU
RESEARCH SCHOLAR

Department of Chemistry
Kurukshetra University, Kurukshetra
 CONTENTS

•Catalysis and its importance?

•Nanocatalysis
•Working of heterogeneous catalyst
•How to choose a best catalyst for the
reaction?
•References
 What is Catalyst

catalyst is a substance which can alter the rate of reactions, and yet
itself will return to its original form without being consumed

Three key aspects of catalyst action

1 taking part in the reaction
• it will change itself during the process by interacting with other
reactant/product molecules

2 altering the rates of reactions

• in most cases the rates of reactions are increased by the action
of catalysts; however, in some situations the rates of undesired
reactions are selectively suppressed

3Returning to its original form

• After reaction cycles a catalyst with exactly the same nature is
‘reborn’
 EFFECTS OF CATALYSTS

Catalysts work by providing…

“AN ALTERNATIVE REACTION PATHWAY WHICH HAS A LOWER
ACTIVATION ENERGY

WITHOUT A CATALYST WITH A CATALYST

 TYPES OF CATALYSIS
Homogeneous catalysis
Reagents and catalyst are all in the same phase (typically all are in
solution).

Heterogeneous catalysis ('surface catalysis')

Reagents are in a different phase from the catalyst - usually the
reagents are gases (or liquids) and are passed over a solid catalyst

Biocatalysis
Using enzymes to catalyse a reaction
 HOMOGENOUS CATALYSIS
•The catalyst is in the same phase as the reactants and products.

•key reactions are reductive elimination and oxidative addition.

copolymerization of limonene oxide and CO2, catalyzed by β-

diiminate–zinc acetate complex
 HETEROGENOUS CATALYSIS
•The catalyst is in the same phase as the
reactants and products.

•key reaction in heterogeneous catalysis is

adsorption
Heterogeneous catalysis of propene to propane
 HOMOGENOUS VS HETEROGENOUS
Heterogeneous
Readily separated 
Readily recycled / regenerated 
Long-lived 
Cheap 
Lower rates (diffusion limited) 
Sensitive to poisons 
Lower selectivity 
High energy process 
Poor mechanistic understanding 
Homogeneous
Difficult to separate 
Difficult to recover 
Short service life 
Expensive 
Very high rates 
Robust to poisons 
Highly selective 
Mild conditions 
Mechanisms often known
 BIO-CATALYSIS

•OCCURS IN BIOLOGICAL SYSTEMS

•ENZYMES ACT AS CATALYST IN THE CATALYTIC PROCESS

•SPECIAL CASE OF HETEROGENOUS CATALYSIS

•THE BIOSYNTHETIC ROUTE IS MORE

COMPLEX THAN TRADITIONAL PATHWAY
EXTREMELY EFFICIENT
Synthesis of adipic acid via two alternative Process
 CATALYST MARKET
catalysts are the workhorses of chemical transformations in the
industry and important for the sustenance of world's economy
 NANO-CATALYSIS
• An emerging field which is at the interface between
homogenous and heterogeneous catalysis

•catalyzed by nanoparticles

•If nanoparticles (NPs) are dispersed in solutions then

process belongs to homogeneous catalysis domain often
referred to as ‘colloidal catalysis’

if NPs are immobilized on solid support the process

falls in the domain of heterogeneous catalysis
HETEROGENEOUS
CATALYSIS
AN INRODUCTION N
 Steps of Catalytic Reaction

- Diffusion of Reactants (Bulk to Film to Surface)

- Adsorption
- Surface Reaction
- Desorption & Diffusion of Products
(a) Adsorption of reactant on the catalyst
when the molecule is present at an infinite distance from the surface, there is no
attraction between the molecule and the surface hence the molecule is at zero
potential energy

as the molecule starts coming close to the catalyst surface, Van der Waals forces of
attraction develop between reactant molecules and surface, and the molecule
becomes “physically adsorbed

Hydroren molecule breaks into gaseous hydrogen atom due to a much greater force of
attraction between hydrogen atom and the metal surface, compared to the hydrogen
molecule and will be able to form a metal-hydrogen bond, hence get adsorbed to the
surface with a heat of adsorption -∆Hc (chemisorption curve)
 LJP ENERGY DIAGRAM

LJP diagram for the adsorption of hydrogen molecule (physical adsorption) and hydrogen
atom (chemisorption) on metal surface
When surface becomes covered by hydrogen (Figure 8), the minimum of the chemisorption
curve decreases in magnitude (dotted curves 1, 2, 3), due to which with the curves intersect
above the energy zero and hence for further adsorption, activation energy is needed

Extension of Lennard-Jones potential energy diagram showing the effect of

increasing hydrogen surface coverage on adsorption.
 SURFACE REACTION
The surface catalyzed bimolecular reactions can
follow two mechanisms

Langmuir–Hinshelwood Mechanism

Eley-Rideal Mechanism:
 Langmuir–Hinshelwood Mechanism
both the reacting species (A & B) firstly get adsorbed on the catalyst surface at different
catalytic sites and later on these adsorbed species undergo surface reactions leading to the
product

Rate of reaction, R = k θAθB

 Eley-Rideal Mechanism:
one reacting partner (A) get adsorbed on the catalyst surface and then react with other reacting
partner (B) in gas phase resulting in product formation

Rate of reaction, R = k θAPB