Heterogeneous Catalysis

Most Heterogeneous Catalysts are Supported Catalysts

Heterogeneous Catalysis
Sample Reactions Catalyzed by Supported Catalysts

Heterogeneous Catalysis
Economic Importance of Supported Catalysts
catalyst employment, without catalyst without Catalyst useemployment, without automobile industry automobile industry automobile industry
Oil Oil processing processing 37% 37% others others 4% 4% Chemical Chemical industry industry 59% 59%

Worth ofthe the assigned catalysts in Catalyst value in Mio. USD in Worth of assigned catalysts 1982(estimation) (1982 estimate) 1982(estimation)
valuesin inmillions millionsUS US values
west west europe europe 460 460 Japan Japan 145 145

USA USA 1450 1450

Effectof ofthe the useof ofcatalysts catalysts Effect use Economic leverage of Catalysts
costof of cost catalyst catalyst 1% 1%

Value of Worththe the Worth catalytically produced produced manufactured products products products 99% 99% 99%

Heterogeneous Catalysis
Properties of a Good Catalyst (1) good activity (2) high selectivity (3) long operating life (simple regeneration) (4) compatibility (low DP, easy separation) (5) robust (6) low cost
2H2 + O2
catalyst

2H2O

2H2+O2

Transition complex 2H2O

catalyst

ln k
good catalyst w/o catalyst

poor catalyst

1/T

Heterogeneous Catalysis
Chemical Reactions are Catalyzed on Surfaces (1) adsorption (2) surface diffusion (3) reaction (4) desorption

reaction coordinate

Heterogeneous Catalysis
Structure of Supported Catalyst

Heterogeneous Catalysis
Supported Catalyst Using high surface are porous support:
(1) ensures large catalyst surface area per unit weight and unit volume of catalyst, (2) provides anchorage for the active sites, (3) prevents sintering of active sites,

But poses problems in term of:

(4) diffusion of reactants and products to and from the active sites, (5) addition and removal of heat from the active sites, (6) actual utilization of catalyst can be low.

Therefore: Temperature and Concentration Gradients are Present in Catalyst Pellet

internal (pore) diffusion > external heat transfer > external (film) mass transfer > internal heat conduction

Heterogeneous Catalysis
Processes in Supported Catalyst
(1) External or film diffusion of reactant molecule(s) (2) Internal or Pore diffusion of reactant molecule(s) (3) Adsorption at an active site (4) Surface Reaction (5) Desorption from the active site (6) Internal pore diffusion of product molecule(s) (7) External diffusion of product molecule(s)

Pore Diffusion
Grahams Experiment

Porous plug

r JA MB r = MA JB

Pore Diffusion
Transport Mechanism in Pore Channels

a) Molecular diffusion, b) Knudsen diffusion, c) viscous flow, d) surface diffusion, e) mass transfer by capillary condensation, f) configurational diffusion

Pore Diffusion
Transport Mechanism in Pore Channels Molecular Diffusion
simple diffusion in the gas space of porous structure valid at low pressures and in large pores (with respect to mean free path, e.g. >100 nm at 100 kPa)

Fick`s law:
for binary or dilute systems
e JA = De AB gradC A = D AB

P dC A gradX A = De AB RT dy

with :

DmA =

(1 x A )

x /D
i=1, i A i

Ai

Pore Diffusion
Transport Mechanism in Pore Channels Knudsen Diffusion
Collisions with pore walls dominate over those with other molecules Valid for low pressures and in narrow pores (with respect to mean free path, l [nm]=10000/P [kPa] )

Kinetic Theory of Gases:

e r DkA JA = grad pA RT d 8RT with: DkA = p 3 MA e = DkA

Transient region

(0,1 < / d < : 10 ) p

(Bosanquet-interpolation)

D =

DkA k

1 1 1 + D D kA Am

Effective diffusion coefficient determined by using the Wicke-Kallenbach-method

Pore Diffusion
Knudsen Diffusion Wicke-Kallenbach Method
A A (+ B)

P=0

A (+ B)

Parameters for pore structure: K0 , K1

Pore Diffusion
Transport Mechanism in Pore Channels Configurational Diffusion
Pores with molecular dimensions (0.3 -1 nm) Strong wall-molecule-interaction (Sorption) Important for microporous catalysts, e.g. Zeolites 10-8<D2-5 nm<10-7 m2/s but 10-17<D< 1 nm<10-13 m2/s

a Dcd = Dm 1 rp

2 +n

log 10 (D cd /D m ) = 2(a/r p )
where 2a = molecular size < dp, n = 2 pore axis and an activation energy of 12 45 kJ/mole

Pore Diffusion
Configurational Diffusion Dominant diffusion mechanism in zeolites
High resolution TEM picture of ZSM-5
1.00E-10

1.00E-11

D (cm 2/s)
1.00E-12 1.00E-13 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Carbon Number

Pore Diffusion
Molecular Diffusion Stefan-Maxwell Equation Fick`s law
e JA = D AB

dC A dy

s P x J x J grad xA = i A e A i RT DAi i=1 i A

De AB =
D AB =

D AB
1 W 3

(0,2 < < 0,8; 3 < < 5 )

k bT = [m] 2 2 P ~ 10 -7 m W= 8RT [m / s] M ~ 500m / s

~ 10 -5 m2 / s

Pore Diffusion
Magnitude of Diffusion Coefficients Molecular, Knudsen and Configurational
Molecular Gases Knudsen

Liquid Configurational

Pore diameter ()

Pore Diffusion
Surface Diffusion
High mobility of adsorbed molecules on the surface Favoured in micropores, by high temperatures, at low partial-/ total-pressure and a high degree of coverage.

Js = -

DsA k Sk D S f ' (C A ) grad CsA = sA k k gradC A s s

2 1 2 Ds exp( E / RT ) 2 2
hop distance, delay time, vibration frequency E = 0.5Hads

10-9<D2-5 nm< 10-7 m2/s at normal temperatures

Pore Diffusion
Surface Diffusion Typical values of surface diffusion coefficients

log10 D0

Movement of Hydrogen on Tungsten Field Emission Tip

Physisorption

q mRT

chemisorption

Pore Diffusion
Poisseuille Flow
Convection flow due to pressure gradient Dominant in reactions with a large change in volume, z.B. cracking, (de)hydrogenation.

rP fl BP J P = - o grad P = grad P 8 RT
2

DP =

rP2 fl RT 8

Pressure gradients result from contradiction between Graham-relationship for isobaric/ isothermal diffusion and stoichiometry

r Ji Mi = 0
i

r JiMi = 0
i

Pore Diffusion
Coupled Transport Mechanisms there is usually more than one transport mechanism for molecular diffusion
x
Ko, K1 Bo

small pores, low pressure

dpi RT D = Ji dx Die 8RT ; Die = k 0 M i
1 2

x + dx

JD j Jk
p p +dp

large pores, high pressure

D x iJD dpi j x j Ji = RT dx Die i j e ; Dij = k1 Dij

convective flow
Jk = B P dp RT dx

Pore Diffusion
Dusty Gas Model for Porous Solids

1 dp i J iD = + RT dx D ie J ik = x i B P dp RT dx

i j

D x iJ D j x jJ i e D ij

J i = J iD + J ik

Pore Diffusion
Dusty Gas Model Pore structure according to Dusty Gas Model

Assumes relatively uniform pore sizes Uniform pore resistance in the porous matrix

Pore Diffusion
Real Porous Catalysts Have nonuniform pore structure consisting of Macro-, Meso- and Micropores

macropores

micropores

Pore Diffusion
Models of Porous Solids Wakao & Smith Model
Gases passes through (1) Macropore (2) Micropore (3) Micropore then Macropore
2 3 1 3 2 31 3 2

a)

1 a
2
x
y

3 1 3

b)

a (1 a )

(1 a )2 2 a a 1 a

Pore Diffusion
Models of Porous Solids Bethe Network 2D Model

Z=4

Z=3

2-D lattices with different degree of branching (Z)

Z=3

Pore Diffusion
Models of Porous Solids Spherical Aggregates 3D

Cubic

Cubic + Block Pores

Cubic + Cavities

Cubic Sphere

Hexagonal Sphere

Random

Pore Diffusion
Other Models for Porous Solids

Adsorption
Adsorption occurs when an incident an atom or molecule stick on the surface

Adsorption
Physisorption

Adsorption
Chemisorption CO adsorption on platinum

Adsorption
Physisorption versus Chemisorption
Parameter Physisorption Chemisorption

Adsorption
Langmuir Adsorption Model
Assumes a uniform surface and that as long as the incident molecules possess the necessary energy, adsorption will occur on a vacant surface site. adsorption process is completely random, no adsorbate-adsorbate interactions, all sites are equivalent and independent of surface coverage ().

Adsorption
Langmuir Adsorption Model
for n adsorbate species
vacant site

Aj + S Ajads
k-j

kj

kj Ajads Kj = k-j = Aj S Ajads = cj = Kj Aj S

number of sites per gram catalysts

Adsorption
Langmuir Adsorption Model
for n adsorbate species

cj = Kj cj cv = Kj cj

Kj cj cm 1 + Kj cj

j =

1 + Kj cj

Adsorption
CO adsorption on Pd Metal 1

Adsorption
CO adsorption on Pd Metal 2

Adsorption
CO adsorption on Pd Metal 3

Adsorption
CO adsorption on Pd Metal 4 Langmuir adsorption isotherm as a function of [CO] for different K-values

Adsorption
Catalyst Surface Area Measurement 1

Adsorption
Catalyst Surface Area Measurement 2

from the intercept

from the slope

Active sites = Nav x 6.02x1023 x 2.89x10-3 = 17.3x1020

Adsorption
Dissociative Adsorption Oxygen chemisorption on Pd Metal 1

Oxygen adsorption requires the presence of two adjacent vacant sites.

Adsorption
Oxygen chemisorption on Pd Metal 2 Probability consideration
The probability of 2 vacant sites appearing adjacent to one another depends on: (1) concentration of vacant sites, (2) arrangement of vacant sites.

The example above illustrates this points. Sample (Left) Number vacant sites Number of adjacent sites 8(16) 0(24)

Sample (Right) 8(16) 10(24)

Adsorption
Oxygen chemisorption on Pd Metal 3 Probability consideration
The probability of finding a pair of adjacent site in a sample with random coverage is:

Adsorption
Oxygen chemisorption on Pd Metal 4

Adsorption
Oxygen chemisorption on Pd Metal 5
160 K 115 K 110 K

105 K

95 K

54 K

Adsorption
Oxygen chemisorption on Pd Metal 6 Formation of oxygen chain structure

Adsorption
Adsorption of CO and O2 on Pd Metal

Adsorption
Adsorption and Reaction of CO and O2 on Pd Metal

Catalysis
What affects Catalysis ? Catalyst Bulk Structure
Hydrodesulfurization of thiopene

1.5 HDS activity (x102/mol/g/h)

10

0.5

Topse, Clausen, Massoth Hydrotreating Catalysis, Science and Technology (Anderson and Boudart (Eds.), Springer (1996).

0 1 2 3 Number of Co edge atoms (x1020/g catalyst)

Catalysis
What affects Catalysis ? Catalyst Surface Structure
Heat of adsorption [kJ/mol]
400 350 300 250 200 150 100 50 0 0 1 2 3 4 5 6 7 8

Cu/MgO Ag/MgO Pb/MgO

M etal coverage [M L]

Larsen, Starr, Campbell, Chem.Thermodyn. 33, 333 (2001) Brown, Kose, King, Chem. Rev. 98, 797 (1998).

Catalysis
What affects Catalysis ? Electronic State CO TPD shift Core level shift

Goodman and Rodriguez, Science 279 (1992) 897

Catalysis
What affects Catalysis ? Electronic State

Correlation between adsorption energies and activation barriers and the d-band center

Mavrikakis , Hammer, Nrskov Phys. Rev. Lett. 81, 2819 (1998)

Catalysis
What affects Catalysis ? Chemical Composition
1,0 0,8

Measured overages of CO on the alloy electrodes with 100 ppm CO/H2

M. Watanabe et al., Phys. Chem. Chem. Phys. 3 (2001) 306

1-co
Pt M

0,6 0,4 0,2 0,0

Calculated changes in CO adsorption energy

2,0 1,0

-d, eV

1,5 1,0 0,5 0,0

0,6 0,4 0,2 0,0

S. Gottesfeld et al., J. Electrochem. Soc. 148 (2001) A11.

-0,5

-0,2

Pt Fe Co Ni Cu Ru Rh Pd Ag Ir Substrate M

Au

Christoffersen, Liu, Ruban, Skriver, Nrskov, J.Catal. 199, 123 (2001)

ECO , eV

0,8

Catalysis
What affects Catalysis ? Surface Composition and Coverage
Ni/Ru Catalyst
5e-7

Initial sticking probability

Thermal dissociation of CH4 at T = 530 K

4e-7

3e-7

2e-7

1e-7

0 0 1 2

Ni Coverage [ML]
Egeberg, Chorkendorff, Catal. Lett. 77, 207 (2001)

Lessons from biology

Catalysis at ambient temperature and pressure Extreme selectivity Direct coupling of energy into the important reaction coordinate (non-thermal catalysis)

Nitrogenase
N 2 + 8H + + 8e
nitrogenase ATP

2NH 3 + H 2
ADP AlF4-

complex formation

Fe protein MoFe protein 4Fe-4S cluster P-cluster

FeP (MgATP) 2+ MoFeP

nucleotide replacement reduction

k1

k -1

FeP (MgATP) 2 MoFeP

ATP cleavage electron transfer

k4

k2

FeMo cofactor Fe protein

FePox(MgADP) 2 + MoFeP

k3 k -3

FePox (MgADP, Pi ) 2 MoFeP

complex dissociation

Burgess, Lowe, Chem. Rev. 96, 2983 (1996) Schindelin, Kisker, Schlessman, Howard, Rees, Nature 387, 370 (1997)

N2 hydrogenation on FeMoco

Rod, Nrskov JACS 122, 12751 (2000)

Comparing the FeMoco and Ru(0001)

Rod, Logadottir, Nrskov J.Chem.Phys. 112, 5343 (2000)