Catalysis

Catalysis Applications
World catalysts
9 G$ business in 1999
24% for Refining, 24% for Chemicals,
23% for Polymers, 29% for Environment

oxidation

According to Dept. Energy, USA, in

2003
Catalysis & Catalytic processes are
responsible for about 20% of the U.S. gross
domestic product (all goods and services)
the keys to future gains in energy efficiency,
environmental stewardship and attendant
economic prosperity for the country

The twelve principles of Green Chemistry

1. It is better to prevent waste than to treat or clean up
waste after it is formed.
2. Synthesis methods must be designed to maximize the
incorporation of all materials used in the process into
the final product.
3. Whenever practicable, synthetic methodologies
should be designed to use and generate substances
that possess little or no toxicity to human health and
the environment.
4. - - - 9. Catalytic reagents (as selective as possible) are
superior to stoichiometric reagents.
10.- - - -

Early History of Catalysis

Neolithic age ( ~5000B.C.)
Biocatalytic fermentation in wine manufacture
500B.C.
Soap manufacture (hydrolysis of animal fats
with potash lye)
1500A.C.
Alchemists formed sulfuric acid by a
mysterious catalytic process

1831
Pelegrine Phillips (a Bristol vinegar
manufacturer) obtained the 1st known patent
in catalysis for the reaction
SO2 + air SO3 (Pt sponge as catalyst)
The catalyst used now-a-day is V2O5/ SiO2
1835
J.J. Berzelius coined the word catalysis
Greek words catameans down
lysis means splitor break

This new force, which is unknown until now, is

common to both organic and inorganic nature. I do
not believe that it is a force completely independent
of electrochemical affinities; It is more convenient
to give this force a separate name. I would therefore
call this the catalytic force. I would furthermore, call
the decomposition of substances resulting from this
force catalysis, just as the decomposition of
substances resulting from chemical affinity is called
analysis.

1880 Carl Groebe

accidentally broke a thermometer while stirring a
mixture of hot naphthalene and H2 SO4
phthalic anhydride & phthalic acid
dye chemistry

1899 Arrhenius equation k = A exp(-Ea/RT)

1903 Ostward process
2NH3 + 7/2 O 2 2NO2 + 3 H2O (Pt sponge as
catalyst)
HNO3 industry

1909 Ostward (German) received Nobel Prize

for studies of reaction rate over catalysts

1912 Paul Sabatier (French) received Nobel Prize

for studies of catalytic hydrogenation of organic
compounds

1915 Haber Process

N2 + 3 H2 2 NH3 (Fe catalyst)
1919 Fritz Haber (German) received Nobel Prize
1920 Sabatier published the 1st book on catalysis
1923 Methanol synthesis
CO + 2 H 2 CH3OH (Cr2O3-ZnO catalyst)
1930 Fischer-Tropsch Process
CO + H2 (CH)n (Fe catalyst)

 1932 Langmuir (USA) received Nobel Prize

For surface chemistry and Langmuir isotherm

1936 Modern era in catalysis

Catalytic cracking of petroleum (acid treated
clays as catalyst)
BET surface area
Deuterium discovery isotope research

1963 Ziegler (German) & Natt (Italian)

received Nobel Prize for stereoregulated
polymerization catalyst

Three Classes of Catalysts

Heterogeneous- The catalyst and the
reactants are in different phases
Homogeneous- The catalyst and the
reactants are in the same phase
Biological - Enzymes

Effect of Catalyst on Reaction Profile

and Activation Energy
Reaction profiles for the
uncatalyzed and catalyzed
decomposition of ozone
Homogeneous Catalysis

Homogeneous Catalysis
Production of acetic acid
1916 acetyleneacetaldehydeacetic acid
1950-1960 oxidation of n-butane or naphtha
1955 homogeneous methanol carbonylation use
Ni catalyst by BASF
1960 iodide-promoted CO catalyst under 2300C
600atm yield 90%
1970 Monsanto synthesis use Rh complex
(180-2200C 30-40atm) yield 99%
1980 Celanese and Daicel improve Monsanto
process adding LiI or NaI
1996 use Ir-based process improved Celanese process
1997 direct oxidation of ethylene by Denko

Production of acetic acid

Methanol carbonylation- Rh catalyzed methanol carbonylation

Rh complex

CH3OH + CO

180-2200C
30-40atm

CH3COOH

r.d.s

Rate [cat.][CH3I]

14-15wt.% of H2O is required

Enzyme Catalysis
Enzymes are high-molecular-mass proteins that
usually catalyze one specific reaction or a set of
quite similar reactions but no others.
Extremely high selectivity
The reactant substance (S), called the substrate,
attaches itself to an area on the enzyme (E) called
the active site, to form an enzyme-substrate
complex (ES).
The rates of enzyme-catalyzed reactions are
influenced by factors such as concentration of the
substrate, concentration of the enzyme, acidity of the
medium, and the temperature.

Induced-fit Model of Enzyme Action

Lock and key Model by

Emil Fischer in 1894

Effect of Substrate Concentration

on Rate: [Enzyme] = Constant

Effect of Enzyme Concentration

on Rate: [Substrate] = Constant

Enzyme Activity as a Function

of Temperature

Heterogeneous Catalysis
Many reactions are catalyzed by the surfaces of
appropriate solids.
Steps in heterogeneous catalytic reactions
1. Diffusion to the surface
2. Adsorption of reactants
3. Surface diffusion of reactants
4. Surface reaction
5. Surface diffusion of products
6. Desorption of products
7. Diffusion away from the surface
Heterogeneous catalysis requires balance of
adsorption, reaction, and desorption
Catalyst strongly adsorbing > no rxn.
Catalyst weakly adsorbing > no rxn.

A Surface-Catalyzed Reaction

Nanostructured Materials ( <100 nm)

Nanostructures represent the transition from atom to
solid.
It is essential to obtain particles or pores with uniform
diameters and shapes and, for the purpose of particular
applications, to arrange and embed them in a
superstructure.
Size quantization effects, high number of surface
atoms, and special surface states.
Special optical, electronic, magnetic, and chemical
properties
Good applications in the areas of signal transmission,
data and energy storage, as well as catalysis.

Catalytic Reaction Steps

O2
CO 2

CO
Precursor
Adsorption

Desorption

Surface
reaction
Surface
diffusion

Rxns catalyzed by Metals

Catalyst

High
activity

H-D exchange

most trans. metals

W, Pt

hydrogenation

Group

hydrogenolysis

Group

skeletal isomerization of (HC)n

Pt, Ir, Pd, Au

Pt

Pt metals

Ru, Rh, Pd
Os, Ir, Pt

double bond shift

Group

dehydrogenation

oxidation
+O

CH2=CH2

+O2

O
CH2

CH2

CH3OH
HCHO
+O2
CO
CO2
Ostwald process
850oC
(i) 4NH3 +5 O2
4NO + 6H2O
N2 +2CO2
2NO + 2 CO
CH4 + H2O

CO + H2

Pd
Pt

Ag
Ag
Au, Pt metals

Pt

Pt metals
Pt metals

Pt
Rh

Ni, Co, Pt metals

Ni,Pt

Transition Metal oxide catalysts

Rxn

Catalyst

Propylene acrolein + acrylic acid

Cu2O or multimetallic oxide

e.g. Bi2O3-MoO3

O2, NH3

C3H6

CH2 CH CN + H2O

One-step ammoxidation
to acrylonitrile

C4H8 +
butane

C4H8

Oxidative
dehydrogenation

1
O2
2

exo
H < 0

C4H 6 + H2O

butadiene

C4H6 + H2

dehydrogenation

H > 0
endo

Complex metal molybdates

or multimetallic oxide
e.g. CdMoO4,
M8FeBi (MoO4)12O12
Co2+, Ni2+
Ferrite spinels
e.g. MnFe2O4, Zn(Cr 2-xFex)O4
metal catalyst, high temp.
easily coking

Transition Metal oxide catalysts (continue)

Rxn

Catalyst

Naphthalene or o-xylene + air

phthalic anhydride

Supported V2O5

n-butane maleic anhydride

(VO)2P2O7

Butene (or benzene) + air

maleic anhydride

(VO)2P2O7 (V2O4/MoO3)

SO 2 +

1
O2
2

SO3

H2SO4

V2O5 + K2SO4 /SiO2

CH3OH lean Fe2O3-MoO3
CH3OH rich Ag

Solid acid catalysts

(i) alumina & acid-treated clays
(ii) alumino-silicate (incorporation of alumina in silica)
silica-alumina amorphous
(iii) protonated zeolites behave as highly acidic solutions
crystalline
shape selectivity
acid amount no. of Al
acid strength 1 / no. of Al
(iv) super acids
TiO2
ZrO2
Fe2O3

H2S
+ SO4-2
SO2

calcination

H0
-14.5
-16.0
-12.9

Acid
Strength

Acid-Catalyzed Rxns
Isomerization (alkene double-bond isomerization;
trans, cis-isomerization)
Alcohol dehydration
Polymerization
Cracking
Skeletal isomerization
CH3
CH3
CH3
Alkylation e.g.
CH3
CH3
+

+ CH3OH

+
CH3

Disproportation

CH3
CH3

CH3

CH3

CH3
CH3

+
CH3

Acylation

CH3

O
CH3 C O CH3
+
O
CH3 C Cl

O
C CH3

increases

Solid basic catalysts less used, and less

developed
MgO (/Li2O), CaO
K/Al2O3
KNH2/Al2O3
M-zeolites (M: Li < Na <K < Rb< Cs specific activity )

Base-Catalyzed Rxns

CH3CH CH2 + H2O

O

OH

dehydrogenation

CH3CH2CH3

aldol condersation

CH3CH2CH3 + H2

O
CH3CH2CH3

acid-catalyzed

base-catalyzed

OH

CH3CCH2C

CH3

CH3
O

- H2O

CH3CCH C

CH3

CH3

Side-chain alkylation with methanol

CH2CH3

CH3
+ CH3OH

CH2 CN + CH3 OH

+ H2O

623K

CHCN + H2 O
CH3

Nanotechnology of Catalysis

Catalysts are perhaps

the first industrial
nanotechnology
2-10 nm particles
(sometimes larger) on
high surface area
support (Al2O3, SiO2)
Automotive catalyst:
nm Pt on -Al2O3

Catalyst Particles
Catalytic reactions occur on catalyst surfaces
Small particles maximize surface area
- optimize use of catalysts
(more metal atoms at surface)
Catalyst dispersion
fraction of catalyst atoms
at surface (10-40%)

Catalyst Turnover

Turnover rate [=] s1: number of reaction cycles completed

at a catalyst site per second
Reactive site

O2

2 CO 2

2 CO

O
C

O
C

Turnover

Automotive Emission Control

carbon monoxide (CO, 0.5 vol.%)

unburned hydrocarbons (HC, 350 vppm)
nitrogen oxides (NO x, 900 vppm)
hydrogen (H2, 0.17 vol.%)
water (H2O, 10 vol.%)
carbon dioxide (CO2, 10 vol.%)
oxygen (O 2, 0.5 vol.%)
CONOxHC

Automotive Emission Control

Largest use of Pt, Pd and Rh industrially
Example of typical heterogeneous catalytic
reaction
Three-way catalyst: Pt/Pd/Rh on CeO2

Pt/Pd: CO + 1/2 O2 > CO2

Pt/Pd: HC + O2 > CO2 + H2O
Rh:

NOx + HC(CO) > N2 + CO2 + H2O

The Catalytic Converter

The catalytic converter consists of Rh, Pt and Pd
particles on an Al 2O3/CeO2 wash-coat deposited on a
monolith of cordierite

Three Way Converter

100
HC
Conv. %

CO
stoic
NOx

Fuel
0
14.3

Computer

A/F ratio

Exhaust
Catalyst
Engine

14.6

Oxygen
sensor

Air
Accelerator

Pt/Pd/Rh
Ceria washcoat

14.9

Catalyst Support Effects

Note cyclic operation of catalytic converter
Fuel lean: CO, HC oxidation
Fuel rich: NOx reduction
Yet oxidation and reduction continue even when
the A/F mixture favors the opposite reaction!
How does this occur?
CeO2 acts as an oxygen storage medium
Fuel rich: Oc + Ce3+ > Ce4+ (i.e. CeO2)
Fuel lean: CeO2 > Ce3+ + O

Nanoscale Effects in Catalysis

Are catalyst particles simply small versions of the
catalyst material?
Does the nanoscale influence catalytic properties
beyond simply presenting more surface atoms?
What possibilities exist for nanoscale modification
of catalyst behavior?
1. Modification of electronic structure
2. Interaction of different structure surfaces
3. Spill-over effects/other support interactions
4. Variation in fluid phase transport properties

Fuel cells
Liquid electrolyte : AFC, PAFC, MCFC
solid electrolyte: PEMFC, SOFC
Low temperature: AFC, PAFC, PEMFC
high temperature: MCFC, SOFC

Fuel cells

Fuel cells

Fuel cells
Concept of solid oxide fuel cell (SOFC)

Fuel cells
Concept of proton-exchange membrane fuel cell PEMFC

The catalysts for fuel cells

 Electrode catalyst supports:

@ AFC: carbon, Ni- or Ag-based
@ PAFC: carbon
@ MCFC: Ni-based cement
@ SOFC: Ni-YSZ cement, LSM/YSZ
@ PEMFC: carbon
Fuel cells with non-hydrogen fuel
@ direct methanol FC: Pt-Ru/carbon, Pd-Ru/carbon
electrode catalysts
@ CH4, gasoline as fuels: adding component of oxidation
catalyst into anode

Catalyst Size Effect- I

Figure 2. (a) Cyclic voltammograms of carbon-supported Pt catalyst samples

recorded in 0.1 M HClO4 solution; T= 20
C, scan rate 50 mV/s; currents are
normalized to the measured Pt surface area (Hupd charge after double layer
correction); HRTEM images of a carbon-supported Pt nanoparticle (b), and the
nanostructured Pt film supported on organic whiskers (c).
J. AM. CHEM. SOC. 127, (2005) 6821

 EXAFS of Pt/C and Pt-alloy/C catalysts

[S. Mukerjee, J. McBreen, J. Electrochem. Soc. 146 (1999) 600.]
Pt/C
0.22

Pt-alloy effects
Effect of change in
potential of 0-0.54 V

Change in dband density

Pt/Ni/C
Pt d-band
density

Pt/Co/C
Pt/Fe/C
Pt/Cr/C

0
2

10

particle size / nm

2.66

2.78

Pt-Pt bond distance / nm

Pt/Cr/C optimal for O2 redn. due to optimal

d-band vacancy

Catalyst Size Effect- II

facile
Active sites
on edge

demanding
Active sites
on terrace

TOF = (AR)/(FE)
Atomic rate

Fraction expose

structure-insensitive

structure-sensitive

Reaction on Nanocatalysts
H2/O2 reaction at 1000 K
(nonflammable mixture in Ar)

[S. Johansson, K. Wong, V.P.

Zhdanov, B. Kasemo, J. Vac. Sci.
Tech. A 17 (1999) 297.]

H2 + 1/2 O2 > H2O

130 nm Pt/CeO2 fresh and
after 10 min of reaction

Equilibrium Particle Shape

Reaction alters particle
shape!
Polycrystalline particles
become crystalline
Large particles disintegrate to
faceted crystals

500 nm Pt/CeO2 (a) fresh and

(b) after 10 min of reaction

Influence of Surface Reaction

Role of oxygen as reactant
- Oxygen adsorption weakens Pt-Pt bonds
- Pt (in oxide form) becomes more mobile
- Effects not seen for H2, H2O
Energy transfer from reaction
- Adsorption highly exothermic (2.5 eV/t.o.)
- High reaction rates (t.o. 103!)
Local temperature increase

Nano-porous materials

Angew. Chem. Int. Ed. Vol. 41, pp. 688-714 (2002)

Development of Zeolites
1950s
Linde company; Synthetic A-type zeolite for separation of
normal and branched paraffins
1960s
X and Y-type zeolites for catalytic cracking
1968
First use of Shape Selectivity properties of zeolites in
selective hydrocracking on erionite
In the past 40 years
Zeolites are used in refining and petrochemicals worldwide.
Many synthetic zeolites are prepared.
1998
160 x 103 tons in catalysis applications

Shape-Selectivity:
Catalytic reactions in
Molecular Sieves

Polymerization in Confined Space

Adsorption of Monomer in Vapor Phase

Conducting Polymerization
Control of Polymer Morphology and Physical
Properties
Molecular blending of different polymers

Extrusion polymerization: Catalyzed

synthesis of crystalline linear polyethylene
nanofibers within a mesoporous silica
Science; 285 (1999) 2113.

Modify Meso-Pore Properties By:

Direct Synthesis

Changes Pore Diameter by Change in Surfactant Chain

Length
Changes Pore Diameter by Addition of Solubilization Agents
Changes Reactivity by Co-precipitation with Functional
Silane

Post Functionalization

Silylation Changes Pore Diameter and Sorption Properties

Changes Reactivity by Adding Reactive Species

Grafting of Sulphonic Acid Groups on

Nano-porous Materials

Si-OH
Si-OH

H3CO
H3CO Si
H3CO

SH

Si

SH

Si-OH

O
H 2O2

O
O

O
Si

OH
S
O

MC M-SO 3H

Summary
Catalysts are an existing nanotechnology
Nanotechnological aspects of catalysis only
just beginning to be understood
More effects to explore
- Modification of electronic structure
- Interaction of facets
- Interaction with support (spillover effects)
- Mass transport resistances
- Confined space reactions and catalysis