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CBE 40445

Lecture 15
Introduction to Catalysis
William F. Schneider
Department of Chemical and Biomolecular Engineering
Department of Chemistry and Biochemistry
University of Notre Dame

wschneider@nd.edu
Fall Semester 2005

W. F. Schneider CBE 40445


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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W. F. Schneider CBE 40445


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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W. F. Schneider CBE 40445


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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W. F. Schneider CBE 40445


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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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”  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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W. F. Schneider CBE 40445


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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W. F. Schneider CBE 40445


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

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W. F. Schneider CBE 40445


Types of Catalysts: Crystalline Microporous
Catalysts

 Regular crystalline structure


 Porous on the scale of molecular dimensions
 10 – 100 Å
 Up to 1000’s m2/g surface area
 Catalysis through
 shape selection
 acidity/basicity
 incorporation of metal particles

10 Å
100 Å

Zeolite (silica-aluminate) MCM-41 (mesoporous silica)


Silico-titanate
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W. F. Schneider CBE 40445


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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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
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W. F. Schneider CBE 40445


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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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 Pt, Rh, Pd
own one! Alumina, ceria, lanthana, …
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W. F. Schneider CBE 40445


Length Scales in Heterogeneous Catalysis

Mass transport/diffusion Chemical adsorption


and reaction
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W. F. Schneider CBE 40445


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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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 / 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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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

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W. F. Schneider CBE 40445


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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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,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 = 1/6
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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

ratea  ka PA N * rated  kd NA


KPA
Site conservation
+
Equilibrium A  , K  ka kd
θA + θ* = 1 rateads = ratedes 1  KPA
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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
200
100 300 400 100 200 300 400
Pressure (torr) Pressure (torr)
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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

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W. F. Schneider CBE 40445