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 (新石器時代 ~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 “cata”means “down”
“lysis” means “split”or “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 acetylene→acetaldehyde→acetic 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 CH3COOH
180-2200C
30-40atm

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 CO 2
Precursor
Adsorption
Desorption

Surface
reaction
Surface
diffusion
 High
Rxn’s catalyzed by Metals Catalyst
activity
H-D exchange most trans. metals W, Pt
hydrogenation Group Ⅷ
hydrogenolysis Group Ⅷ
skeletal isomerization of (HC)n Pt, Ir, Pd, Au Pt
Pt metals
Ru, Rh, Pd
double bond shift Os, Ir, Pt
Pd

dehydrogenation Group Ⅷ Pt
oxidation O Ag
+O 2
CH2=CH2 CH2 CH2
+O2 Ag
CH3OH HCHO
+O2
CO CO2 Au, Pt metals Pt
Ostwald process
850oC
(i) 4NH3 +5 O2 4NO + 6H2O Pt metals Pt
2NO + 2 CO N2 +2CO2
Pt metals Rh
CH4 + H2O CO + H2
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 Complex metal molybdates

C3H6 CH2 CH CN + H2O or multimetallic oxide
e.g. CdMoO4,
One-step ammoxidation
M8ⅡFeⅢBiⅢ (MoO4)12O12
to acrylonitrile

exo
Co2+, Ni2+
Oxidative
∆H < 0
dehydrogenation
1 C4H 6 + H2O
C4H8 + O2 Ferrite spinels
2
butane butadiene e.g. MnFe2O4, Zn(Cr 2-xFex)O4
C4H8 C4H6 + H2 “metal” catalyst, high temp.
dehydrogenation ∆H > 0 easily coking
endo
Transition Metal oxide catalysts (continue)
Rxn Catalyst
Naphthalene or o-xylene + air
Supported V2O5
→ phthalic anhydride

n-butane → maleic anhydride (VO)2P2O7

Butene (or benzene) + air (VO)2P2O7 (V2O4/MoO3)

→ maleic anhydride

1 V2O5 + K2SO4 /SiO2

SO 2 + O2 SO3 H2SO4
2

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 α no. of Al
acid strength α 1 / no. of Al
(iv) super acids
H0
TiO2 H2S -14.5
ZrO2 + SO4-2 calcination -16.0
Fe2O3 SO2 -12.9
Acid-Catalyzed Rxn’s Acid
Strength
Isomerization (alkene double-bond isomerization;
trans, cis-isomerization)
Alcohol dehydration
Polymerization
Cracking
Skeletal isomerization
Alkylation e.g. CH3 CH3 CH3 CH3
CH3
+ CH3OH + +
CH3

Disproportation CH3

CH3 CH3 CH3 CH3

CH3
2 + + +
CH3
CH3 increases
O
Acylation O
C CH3
CH3 C O CH3
+ O
CH3 C Cl
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 Rxn’s CH3CH CH2 + H2O acid-catalyzed
OH O
dehydrogenation CH3CH2CH3 CH3CH2CH3 + H2 base-catalyzed
O O OH
aldol condersation CH3CCH2C CH3
CH3CH2CH3
CH3
- H2O
O
CH3CCH C CH3
CH3

Side-chain alkylation with methanol

CH3 CH2CH3

+ CH3OH + H2O

CH2 CN + CH3 OH CHCN + H2 O

623K
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 γ-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 [=] s–1: number of reaction cycles completed
at a catalyst site per second
Reactive site O2
2 CO 2

O O
O C O C Turn- O O
over

2 CO
 Automotive Emission Control

車輛所排放的廢氣是造成空氣污染的最大來源之
一，一般引擎所排放的廢氣主要組成為：
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.%)
其中對環境危害最嚴重的是CO，NOx，及HC。
 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 14.6 14.9

Computer A/F ratio

Exhaust
Catalyst
Oxygen
Engine sensor Pt/Pd/Rh
Ceria washcoat
Air
Accelerator
 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 Pt-alloy effects

Effect of change in
Pt/Ni/C
0.22 potential of 0-0.54 V
Pt/Co/C
Change in d- Pt d-band Pt/Fe/C
band density density Pt/Cr/C

0
2 4 10 2.66 2.78

particle size / nm 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)
Fraction expose
Atomic rate
 structure-insensitive

structure-sensitive
 Reaction on Nanocatalysts
H2/O2 reaction at 1000 K [S. Johansson, K. Wong, V.P.
Zhdanov, B. Kasemo, J. Vac. Sci.
(nonflammable mixture in Ar) 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 H3CO O
H3CO Si SH
O
Si-OH H3CO Si SH
O
Si-OH

O
O
O Si OH
H 2O2
O S
MC M-SO 3H
O
 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