CBE 40445

Lecture 15
Introduction to Catalysis
Developed by Prof. Schneider1,2
Modified by Prof. Hicks1

1Departmentof Chemical and Biomolecular Engineering

2Department of Chemistry and Biochemistry

University of Notre Dame

Fall 2011

W. F. Schneider CBE 40445

 Importance of Catalysts

Bartholomew and Farrauto, Fundamentals of Industrial Catalytic Processes, Wiley, 2006.

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 What is a “Catalyst”

 A catalyst (Greek: καταλύτης, catalytēs) is a substance that

accelerates the rate of a chemical reaction without itself being
transformed or consumed by the reaction. (thank you Wikipedia)

k(T) = k0e-Ea/RT
Ea′ < Ea
k0′ > k0
Ea k′ > k Ea′

ΔG = ΔG

A+B A+B+
ΔG catalyst ΔG

C C + catalyst

uncatalyzed catalyzed
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 Catalysts Open Up New Reaction Pathways

‡
H O

H2C C
O CH3 OH

C C
CH3 CH3 CH2 CH3
‡
propanone propenol

propenol

propanone
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 Catalysts Open Up New Reaction Pathways

O−

C + H2O
CH2 CH3
OH− −OH−

Base catalyzed
O OH
rate = k[OH−][acetone]
C C
CH3 CH3 CH2 CH3

propanone propenol
‡ ‡

propenol
intermediate
propanone
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 Catalysts Open Up New Reaction Pathways
‡ ‡

propenol
different
propanone intermediate
propenol
O OH
propanone rate = k[H3O+][acetone]
C C
Acid catalyzed
CH3 CH3 CH2 CH3

H3O+ −H3O+
OH

C
+
CH3 CH3

+ H2O
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 Types of Catalysts - Enzymes

 The “Gold Standard” of

catalysts
 Highly specific
 Highly selective
 Highly efficient
 Catalyze very difficult
reactions
 N2  NH3
 CO2 + H2O  C6H12O6
Triosephosphateisomerase
“TIM”  Works better in a cell
Cytochrome C Oxidase
than in a 100000 l
reactor
Highly tailored “active sites”
Often contain metal atoms
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 Types of Catalysts – Organometallic Complexes
 Perhaps closest man has
come to mimicking
nature’s success
 2005 Noble Prize in
Chemistry
 Well-defined, metal-based
active sites
 Selective, efficient
manipulation of organic
functional groups
 Various forms, especially
Polymerization: for polymerization
catalysis

 Difficult to generalize
Termination:
beyond organic
transformations
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 Types of Catalysts – Homogeneous vs.
Heterogeneous

Zeolite catalyst Catalyst powders

Homogeneous catalysis Heterogeneous catalysis

Single phase Multiphase
(Typically liquid) (Mostly solid-liquid and solid-gas)
Low temperature High temperature
Separations are tricky Design and optimization tricky
Newer area of Research:
Tethered Catalysts (maintaining
selectivity of homogeneous catalysts
but tethered to a solid support)
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 Types of Catalysts: Crystalline Microporous
Catalysts

 Regular crystalline structure

 Porous on the scale of molecular dimensions
 3 – 20 Å (microporous), 20-500 Å (mesoporous)
 Up to 1000’s m2/g surface area
 Catalysis through
 shape selection
Applied Catalysis A, 2009, 360, 59-65.
 acidity/basicity
 incorporation of metal particles
 Used as supports for other metal precursors

10 Å 40 Å

MCM-41 (mesoporous silica)

Zeolite (silica-aluminate)
Silico-titanate
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Types of Catalysts: Zeolites

Morphology changes due to additives, quantities, pH, time,

What are zeolites ? etc. Shown below are SEM images of HZSM-5 (5.6 Å pores)
- Aluminosilicates
- microporous ( pores < 20Å)
- Crystalline
- Framework of AlO4 and
SiO4 Td-units (tetrahedral)
- Possess ordered pore
systems
- Acidity arises from
incorporation of Al
Al2O3 source
Neumann and Hicks, 2011.

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All silica ~ weak acidity SiO2/Al2O3 ~ Brønsted acidity
 Types of Catalysts: Zeolites
Sodalite
(SOD)
pores ~3Å

[SiO4 ]4-
[AlO4]5-

Zeolite - A
LTA -cages FAU (LTA)
pores ~ 4Å

Zeolite - X, Y
(FAU)
A● large cage (~ 12Å)
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formed in A and X,Y
 Types of Catalysts: Amorphous Heterogeneous
Catalysts
 Amorphous, high surface area supports
 Alumina, silica, activated carbon, …
 Up to 100’s of m2/g of surface area
 Impregnated with catalytic transition metals
 Pt, Pd, Ni, Fe, Ru, Cu, Ru, …
 Typically pelletized or on monoliths
 Cheap, high stability, catalyze many types of reactions
 Most used, least well understood of all classes

SEM micrographs of alumina and Pt/alumina

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Types of Catalysts: Motivation for Tethered
Catalysts

Traditional Heterogeneous Homogeneous (Soluble)

(Insoluble)  High mobility - active
 Easy to separate  Single type of active
 Multiple types of active site -selective
sites  Control of
 Less mobility / spatially stereochemistry
constricted  Difficult to separate
 Diffusion effects
Tethered
• Insoluble
• Single type of active
site-selective
• Easy to separate
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 Types of Catalysts: Examples of Tethered
Catalysts

H2 NH 2
Zr C
Al Al
Me
OMe
O
Si
OMe
O S O
O
F3C F
F
F SiO2
O
O O Hicks, J. C.; Jones, C. W., Langmuir 2006, 22, 2676.
Si Si Si
Hicks, J. C.; Dabestani, R.; Buchanan III, A. C.; Jones,
R. A. Shiels, K. Venkatasubbaiah and C. C. W., Chem. Mater. 2006, 18, 5022.
J. C. Hicks, B. A. Mullis and C. W. Jones,
W. Jones, Adv. Synth. Catal. (2008)
J. Am. Chem. Soc. (2007) 129, 8426-8427.
350, 2823-2834.

(C6H5)2
(C6H5)2 P
P

Si Cl Q Ir (complex) F Ir (complex)
Zr
N Cl
P(C6H5) P(C6H5)

VS.
OSiMe3
Si Si
OEt OEt
O O O Si Si
O O O O

Hicks, J. C.; Dabestani, R.; Buchanan III, A. SBA-15 SBA-15

C.; Jones, C. W., Inorg. Chim. Acta, 2008. Collaboration between Hicks and Schneider Groups
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 Important Heterogeneous Catalytic Processes

 Haber-Bosch process
 N2 + 3 H2 → 2 NH3
 Fe/Ru catalysts, high pressure and temperature
 Critical for fertilizer and nitric acid production

 Fischer-Tropsch chemistry
 n CO + 2n H2 → (CH2)n + n H2O , syn gas to liquid fuels
 Fe/Co catalysts
 Source of fuel for Axis in WWII

 Fluidized catalytic cracking

 High MW petroleum → low MW fuels, like gasoline
 Zeolite catalysts, high temperature combustor
 In your fuel tank!

 Automotive three-way catalysis

 NOx/CO/HC → H2O/CO2/H2O
 Pt/Rh/Pd supported on ceria/alumina
 Makes exhaust 99% cleaner
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 Heterogeneous Catalytic Reactors
 Design goals
 rapid and intimate contact
Packed Bed between catalyst and
(single or multi-tube) reactants
 ease of separation of
products from catalyst

Fluidized Slurry Catalyst

Bed Reactor Recycle
Reactor

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 FCC: Fluidized Catalytic Cracker

Gasoline Production

Gas oil enters the riser reactor

and is mixed with a zeolite
catalyst (Zeolite Y).

Acid-catalyzed cracking
reactions occur in reactor.

Coke formation occurs quickly

on the catalyst (carbon
deposition).

Catalyst residence time is ~ 1.5

seconds.

Catalyst is separated,
regenerated, and re-injected.

Bartholomew and Farrauto, Fundamentals of Industrial Catalytic Processes, Wiley, 2006.

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 Automotive Emissions Control System

“Three-way” Catalyst
CO  CO2
HC  CO2 + H2O
NOx  N2

Monolith reactor

Most widely deployed

heterogeneous catalyst in
the world – you probably Pt, Rh, Pd
own one! Alumina, ceria, zirconia, …
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 Length Scales in Heterogeneous Catalysis

Mass transport/diffusion Chemical adsorption

and reaction
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 Steps in a Heterogeneous Catalytic Reactor

Diffusion Steps: 1, 2, 6, 7.
Reaction Steps: 3, 4, 5.
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 Characteristics of Heterogeneous Supported
Catalysts
 Surface area:
 Amount of internal support surface accessible to a fluid
 Measured by gas adsorption isotherms
 Loading:
 Mass of transition metal per mass of support
 Dispersion:
 Percent of metal atoms accessible to a fluid

M M M

support
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 Rates of Catalytic Reactions

 Pseudo-homogeneous reaction rate

 r = moles / volume · time

 Mass-based rate
 r′ = moles / masscat · time
 r′ = r / ρcat

 Heterogeneous reactions happen at surfaces

 Area-based rate
 r′′ = moles / areacat · time
 r′′ = r′ / SA, SA = area / mass
TOF (s−1)
 Heterogeneous reactions happen at active sites Hetero. cats. ~101
 Active site-based rate Enzymes ~106
 Turn-over frequency TOF = moles / site · time
 TOF = r′′ / ρsite

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 Adsorption and Reaction at Solid Surfaces

 Physisorption: weak van der Waals attraction of a fluid

(like N2 gas) for any surface
 Eads ~10 – 40 kJ/mol
 Low temperature phenomenon
 Exploited in measuring gross surface area

 Chemisorption: chemical bond formation between a fluid

molecule (like CO or ethylene) and a surface site
 Eads ~ 100 – 500 kJ/mol
 Essential element of catalytic activity
 Exploited in measuring catalytically active sites

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 Comparing Physi- and Chemisorption on MgO(001)
Calculated from first-principles DFT 1.25

1.48
O O
Physisorbed CO2 C
CO2 -2 kcal mol-1 GGA
2-

: :
:O:surf

1.51

1.77 2.10
Mg Chemisorbed SO2
SO2 (“sulfite”)
O -25 kcal mol-1 GGA
O O

:
S

2-
: :
:O:surf
2.60
1.45 1.48
SO3 Chemisorbed SO3
1.66 2.12 (“sulfate”)
-50 kcal mol-1 GGA
O
O O
MgO(001) supercell S

2-

: :
Schneider, Li, and Hass, J. Phys. Chem. B 2001, 105, 6972 :O:surf
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2.58
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 Measuring Concentrations in Heterogeneous
Reactions Kinetics
 Fluid concentrations
 Traditionally reported as pressures (torr, atm, bar)
 Ideal gas assumption: Pj = Cj RT
Rate = f(Pj,θj)
 Surface concentrations Metal particle surface
 “Coverage” per unit area
 nj = molesj / area
 Maximum coverage called monolayer
 1 ML: nj,max = ~ 1015 molecules / cm2
 Fractional coverage
 θj = nj / nj,max
 0 ≤ θj ≤ 1

θj = 1/5
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 Adsorption Isotherms

 Molecules in gas and surface are in dynamic equilibrium

A (g) + M (surface) ↔ M-A
 Isotherm describes pressure dependence of equilibrium

 Langmuir isotherm proposed by Irving Langmuir, GE, 1915

 (1932 Noble Prize)
 Adsorption saturates at 1 monolayer
 All sites are equivalent
 Adsorption is independent of coverage

ratea  ka PA N * rated  kd NA

KPA
Site conservation
+
Equilibrium A  , K  ka kd
θA + θ* = 1 rateads = ratedes 1  KPA
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ●
○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
W. F. Schneider CBE 40445
 Using the Langmuir Isotherm

 Example: CO adsorption on 10% Ru/Al2O3 @ 100°C

PCO (torr) 100 150 200 250 300 400
COads (μmol/gcat) 1.28 1.63 1.77 1.94 2.06 2.21
CO adsorption on Ru/Al 2O3 at 100C CO adsorption on Ru/Al O at 100C
2 3
Non-linear regression Linearized model
2.6 200

2.4 nCO,∞ = 2.89 μmol/gcat

K = 0.0082
2.2

(torr g /mol)
2 150
(mol/g )
cat

cat
1.8

1.6
CO CO
CO

P /n
n

nCO, KPCO PCO P 1

1.4 nCO  100  CO 
1  KPCO nCO nCO, KnCO,
1.2

0.8 50
200100 300 400 100 200 300 400
Pressure (torr) Pressure (torr)
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ●
○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
W. F. Schneider CBE 40445
 Brunauer-Emmett-Teller Isotherm (BET)

 Relaxes Langmuir restriction to single layer adsorption

 Monolayer adsorption; multilayer condensation
 Useful for total surface area measurement
 Adsorption of boiling N2 (78 K)

cz ΔHads/ΔHcond
V 
Vmono (1  z )(1  (1  c) z )
( H ads H cond ) ΔHcond
z P , ce RT
Pvap

ΔHads

Solid Surface

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ●
○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○
W. F. Schneider CBE 40445