CBE 40445

Lecture 15
Introduction to Catalysis
Developed by Prof. Schneider1,2
Modified by Prof. Hicks1
1

Fall 2011

W. F. Schneider

Department of Chemical and Biomolecular Engineering

2
Department of Chemistry and Biochemistry
University of Notre Dame

CBE 40445

Importance of Catalysts

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

W. F. Schneider

CBE 40445

What is a Catalyst
A catalyst (Greek: , catalyts) 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
k > k

Ea

Ea

G = G
A+B

A+B+
catalyst

G
C

G
C + catalyst

uncatalyzed

catalyzed

W. F. Schneider

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Catalysts Open Up New Reaction Pathways

H2C

OH

CH3

C
CH3

C
CH3

CH2

propanone

CH3

propenol

propenol
propanone

W. F. Schneider

CBE 40445

Catalysts Open Up New Reaction Pathways

O
C
CH2

OH

+ H2O
CH3

OH

Base catalyzed
O

OH

rate = k[OH][acetone]

C
CH3

C
CH2

CH3

propanone

CH3

propenol

propenol
intermediate
propanone

W. F. Schneider

CBE 40445

Catalysts Open Up New Reaction Pathways

propenol
different
intermediate

propanone

propenol
propanone
CH3

OH

rate = k[H3O+][acetone]

C
CH3

Acid catalyzed

H 3 O+

CH3

CH3

H3O+

OH
C
+

CH2

CH3

+ H2O

W. F. Schneider

CBE 40445

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
Cytochrome C Oxidase
Highly tailored active sites
Often contain metal atoms

Works better in a cell

than in a 100000 l
reactor

W. F. Schneider

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Types of Catalysts Organometallic Complexes

Perhaps closest man has
come to mimicking
natures success
2005 Noble Prize in
Chemistry
Well-defined, metal-based
active sites
Selective, efficient
manipulation of organic
functional groups
Various forms, especially
for polymerization catalysis

Polymerization:

Difficult to generalize
beyond organic
transformations

Termination:

W. F. Schneider

CBE 40445

Types of Catalysts Homogeneous vs.

Heterogeneous

Zeolite catalyst

Catalyst powders

Homogeneous catalysis

Heterogeneous catalysis

Single phase
(Typically liquid)
Low temperature
Separations are tricky

Multiphase
(Mostly solid-liquid and solid-gas)
High temperature
Design and optimization tricky

Newer area of Research:

Tethered Catalysts (maintaining
selectivity of homogeneous catalysts
but tethered to a solid support)

W. F. Schneider

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Types of Catalysts: Crystalline Microporous

Catalysts
Regular crystalline structure
Porous on the scale of molecular dimensions
3 20 (microporous), 20-500 (mesoporous)
Up to 1000s m2/g surface area

Catalysis through
shape selection
acidity/basicity
incorporation of metal particles

Applied Catalysis A, 2009, 360, 59-65.

Used as supports for other metal precursors

40

10

MCM-41 (mesoporous silica)

Zeolite (silica-aluminate)

Silico-titanate

W. F. Schneider

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Types of Catalysts: Zeolites

What are zeolites ?
- Aluminosilicates
- microporous ( pores < 20)
- Crystalline
- Framework of AlO4 and
SiO4 Td-units (tetrahedral)
- Possess ordered pore
systems
- Acidity arises from
incorporation of Al

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

etc. Shown below are SEM images of HZSM-5 (5.6 pores)

Al2O3 source
Neumann and Hicks, 2011.

2
2 3

All silica ~ weak acidity

SiO /Al O ~ Brnsted acidity

Types of Catalysts: Zeolites

Sodalite
(SOD)
pores ~3

[SiO4 ]4[AlO4]5-

LTA

-cages

FAU

A large cage (~ 12)

formed in A and X,Y

Zeolite - A
(LTA)
pores ~ 4
Zeolite - X, Y
(FAU)
pores ~ 7.4

Types of Catalysts: Amorphous Heterogeneous

Catalysts
Amorphous, high surface area supports
Alumina, silica, activated carbon,
Up to 100s 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

W. F. Schneider

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Types of Catalysts: Motivation for Tethered

Catalysts

Traditional Heterogeneous
(Insoluble)
Easy to separate
Multiple types of active
sites
Less mobility / spatially
constricted
Diffusion effects

Homogeneous (Soluble)
High mobility - active
Single type of active
site -selective
Control of
stereochemistry
Difficult to separate
Tethered
Insoluble
Single type of active
site-selective
Easy to separate

Types of Catalysts: Examples of Tethered

Catalysts

O
O

HN

Si

V
O

Zr
Me

O
O

H2
C
Al

NH 2

Al
OMe

Si

O S O
F3C F
F
F
O
O
O
Si
Si
Si

OMe

R. A. Shiels, K. Venkatasubbaiah and C.

W. Jones, Adv. Synth. Catal. (2008)
350, 2823-2834.

O
SiO2

Hicks, J. C.; Jones, C. W., Langmuir 2006, 22, 2676.

Hicks, J. C.; Dabestani, R.; Buchanan III, A. C.; Jones,
C. W., Chem. Mater. 2006, 18, 5022.

J. C. Hicks, B. A. Mullis and C. W. Jones,

J. Am. Chem. Soc. (2007) 129, 8426-8427.

(C 6H 5)2
P

(C 6H 5)2
P

Si

Si
O

Si
O

Zr

Cl

Cl

Ir (c o m p le x )

P (C 6H 5)

Ir (c o m p le x )

P (C 6H 5)
V S.

OSiMe3
O Et

Si

Hicks, J. C.; Dabestani, R.; Buchanan III, A.

C.; Jones, C. W., Inorg. Chim. Acta, 2008.

OMe

S B A -1 5

O Et

Si
O

S B A -1 5

Collaboration between Hicks and Schneider Groups

W. F. Schneider

CBE 40445

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

W. F. Schneider

CBE 40445

Heterogeneous Catalytic Reactors

Design goals
rapid and intimate contact
between catalyst and
reactants
ease of separation of
products from catalyst

Packed Bed
(single or multi-tube)

Fluidized
Bed

Slurry
Reactor

Catalyst
Recycle
Reactor

W. F. Schneider

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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.

W. F. Schneider

CBE 40445

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
own one!

Pt, Rh, Pd
Alumina, ceria, zirconia,

W. F. Schneider

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Length Scales in Heterogeneous Catalysis

Mass transport/diffusion

Chemical adsorption
and reaction

W. F. Schneider

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Steps in a Heterogeneous Catalytic Reactor

Diffusion Steps: 1, 2, 6, 7.
Reaction Steps: 3, 4, 5.

W. F. Schneider

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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

support

W. F. Schneider

CBE 40445

Rates of Catalytic Reactions

Pseudo-homogeneous reaction rate
r = moles / volume time

Mass-based rate
r = moles / masscat time
r = r / cat

Heterogeneous reactions happen at surfaces

Area-based rate
r = moles / areacat time
r = r / SA,
SA = area / mass

Heterogeneous reactions happen at active sites

Active site-based rate

1
TOF
TOF(s(s1) )
1
Hetero.
Hetero.cats.
cats. ~10
~101
6
Enzymes
Enzymes ~10
~106

Turn-over frequency TOF = moles / site time

TOF = r / site

W. F. Schneider

CBE 40445

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

W. F. Schneider

CBE 40445

Comparing Physi- and Chemisorption on MgO(001)

1.25

Calculated from first-principles DFT

1.48

Physisorbed CO2
-2 kcal mol-1 GGA

C
: :

CO2

2-

:O:surf

1.51

SO2

S
: :

Mg

1.77

Chemisorbed SO2
(sulfite)
-25 kcal mol-1 GGA

2.10

2-

:O:surf
2.60
1.45

SO3

1.48
1.66

Chemisorbed SO3
(sulfate)
-50 kcal mol-1 GGA O
O
S
: :

MgO(001) supercell

2.12

O
2-

:O:surf

Schneider, Li, and Hass, J. Phys. Chem. B 2001, 105, 6972

2.58

W. F. Schneider

CBE 40445

Measuring Concentrations in Heterogeneous

Reactions Kinetics
Fluid concentrations
Traditionally reported as pressures (torr, atm, bar)
Ideal gas assumption: Pj = Cj RT
Rate = f(Pj,j)

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
j = nj / nj,max
0 j 1

j = 1/5

W. F. Schneider

CBE 40445

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

rated kd N A

ratea ka PA N *
Site conservation
A + * = 1

Equilibrium
rateads = ratedes

KPA
, K k a kd
1 KPA

W. F. Schneider

CBE 40445

Using the Langmuir Isotherm

Example: CO adsorption on 10% Ru/Al2O3 @ 100C
PCO (torr)

100

150

200

250

300

400

COads (mol/gcat)

1.28

1.63

1.77

1.94

2.06

2.21

CO adsorption on Ru/Al2O3 at 100C

Linearized model

nCO, = 2.89 mol/gcat

K = 0.0082

2.4
2.2
2

nC O (m o l/gc a )t

200

1.8
1.6
1.4

nCO

nCO, KPCO
1 KPCO

PC O/nC O (to rr cga /t m o l)

2.6

CO adsorption on Ru/Al2O3 at 100C

Non-linear regression

150

100

PCO
P
1
CO
nCO nCO, KnCO,

1.2
1
0.8

50
200
300
400
100
200
300
400
(torr)
Pressure

Pressure
(torr)

100

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)

Vmono

Hads/Hcond

cz
(1 z )(1 (1 c) z )

z P

Pvap

, ce

o
o
( H ads
H cond
)

Hcond
RT

Hads
Solid Surface

W. F. Schneider

CBE 40445