The Concepts of Heterogeneous Catalysis

What is catalysis?

J.W. Niemantsverdriet
Schuit Institute of Catalysis
Eindhoven University of Technology
Lecture presented at
Mumbai University Institute of Chemical Technology
February 2003
What is catalysis
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
A P
B
separation

catalyst
P
bonding catalyst

A
reaction
B

catalyst
 P
potential energy

A + B

A
B

cataly st
P
A B

cataly st P cataly st
cataly st

bonding reaction separation

reaction coordinate
What is catalysis
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
 Langmuir - Hinshelwood Kinetics

1915 Langmuir:
Adsorption Isotherm
1927 Hinshelwood:
Kinetics of Catalytic
Reactions

Cyril Norman Irving Langmuir

Hinshelwood 1881 - 1957
1897 - 1967 Nobel Prize 1932
Nobel Prize 1956

• Consistent with Sabatier’s Principle

• Coverage dependence: Volcano plot
• Temperature dependence: Volcano plot
Reaction Mechanism:
A + * ⇔ Aads equilibrium; KA
B + * ⇔ Bads equilibrium; KB
Aads + Bads → ABads + * r.d.s; k
ABads → AB + * fast

Coverages:
1
θ A = K A pA θ * θB = KB pB θ* θ* = 1 + K p + K p
A A B B

N* k KAKB pA pB
Reaction rate: r=
(1 + KA pA + KB pB )2
 Irving Langmuir
(1881 - 1957)

• worked at General Electrics

• oxygen adsorption on tungsten
filaments of light bulbs
• 1932: Nobel Prize in Chemistry
• Langmuir Adsorption Isotherm:

KA [A]
0A =
1 + KA [A]
Rate of reaction, Activation energy, Order of reaction:

N* k KAKB pA pB
r=
(1 + KA pA + KB pB )2

∂ ln r 2 ∂ ln r
E app
= −R = RT
∂(1 / T ) ∂T
a

= E rds
a + (1 − 2θ A ) ∆H A + (1 − 2θ B ) ∆H B

∂ ln r ∂ ln r
nA = = pA = 1 − 2θ A
∂ ln p A ∂ pA
Rate of a Catalytic Reaction: Eads(A) = Eads(B) = 125 kJ/mol

Pressure Dependence s(B) = s(A) ; Eact = 50 kJ/mol

T = 600 K; pB is fixed
1,2
rate
1.0
normalized rate

1,0
rate
0.8
0,8

0.6
0,6 θB θA θA
0.4
0,4

0.2 θB
θ,

0,2

0.0
0,0
θ*
-1,0 -0,8 -0,6 -0,4 -0,2 0,0 0,2 0,4 0,6 0,8
0.1 1.0 10
reaction order
positive in pA
pA/pB reaction order
negative in pA
negative in pB positive in pB
Rate of a Catalytic Reaction: Eads (A) = 135 kJ/mol
Eads (B) = 125 kJ/mol
Temperature Dependence s(B) pB = 10 s(A) pA
Eact = 50 kJ/mol
1,0
θ*
normalized rate

0,8 θA rate

0,6

0,4

0,2
θB
θ,

0,0
100 300 500 700 900
T (K)
reaction order reaction order
negative in pA positive in pA and pB
positive in pB
 The Sabatier Effect
catalytic activity

optimum interaction
catalyst - adsorbate:
• not too strong
• not too weak

metal - adsorbate bond strength optimum

coverage
Catalysis by Metals: Trends in Reactivity

strong, dissociative adsorption

stable oxides, carbides, nitrides

Cr Mn Fe Co Ni Cu

Mo Tc Ru Rh Pd Ag

W Re Os Ir Pt Au

Weak, molecular adsorption

stable against
oxide, carbide, nitride formation
What is catalysis
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
 Example: CO Oxidation
O2

CO CO2

catalyst
adsorption reaction desorption

What is the most essential thing that the catalyst does ?

a catalyst breaks bonds……...

…...and lets other bonds form

The minimum you need to know about . . . . . .
Molecular Orbitals
Overlap:

atom molecule atom

anti
bonding

much / little overlap

Filling:

bonding
atomic molecular atomic
orbital orbitals orbital
strong weak no bond
 and about . . . . .

Bonding in Metals

4p

energy
sp - band

4s

3d
d-band

atom metal density of states

Work Function: Ionization Potential of a Metal
The Surface Contribution to the Work Function
surface
metal vacuum
+ -
Evac + -
+ -
ϕ +
+
-
-
+ -
EF density

ionic cores electrons

-
distance

ϕ : energy barrier for electrons leaving the surface

Strength of metals:
Filling of bands
EF
EF

10
5d-series
Cohesive Energy (eV)

8 EF
6
4d-series
4

2
3d-series

0
Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Ba La Hf Ta W Re Os Ir Pt Au Hg
 Atomic Adsorption in the ‘Resonant Level Model’
(the simplest description)

EVac Vacuum level

Work function Ionization

energy
EF Fermi level
ea
sp-band

Core level 1

Core level 2

Metal Adsorbed atom Free atom

Jellium has no d-band

(e.g. Al)
 Atom on free-electron metals (no d-band):

Evac Evac Evac

EF
EF
EF

jellium adsorbed free jellium adsorbed free jellium adsorbed free

metal atom atom metal atom atom metal atom atom
 Molecules on free-electron metals (no d-band):
a) b)
Evac Evac

σ* σ*
EF
EF 1s 1s 1s 1s

σ σ

jellium adsorbed free jellium adsorbed free

metal molecule molecule metal molecule molecule
 Atom on d-metal:
a) b)
Evac Evac
antibonding antibonding

EF
EF d-band

bonding bonding

s-band

d-metal adsorbed free d-metal adsorbed free

atom atom atom atom
Molecular Adsorption on a d-metal
σ-orbitals σ*-orbitals

Evac antibonding

σ*
antibonding

EF 1s 1s
bonding

bonding

d-metal adsorbed molecule free molecule

 This picture is the key to understanding
CO adsorption on a d-metal

catalysis in terms of orbital theory

d-5σ d-2π*

Evac antibonding

2π*
antibonding

EF
bonding

5σ

bonding

d-metal adsorbed molecule free molecule

“back donation”
“relieved repulsion” binds molecule to surface
favors on-top adsorption weakens internal CO bond!
often called “donation” favors multiple coordination
a catalyst breaks bonds……...

How?
 Atoms prefer high coordination sites
hcp fcc top bridge
Carbon
on
Rh(111)

1.99 eV

0.67 eV
0.00 eV 0.24 eV

hcp fcc top bridge

Nitrogen
on
Rh(111)

2.13 eV

0.72 eV
0.00 eV 0.14 eV

Paco Ample, Dani Curulla, Josep Ricart, Hans Niemantsverdriet, 2002

Dissociation:

The CO molecule dissociates in the transition state:

optimal overlap between d- and 2π*-orbitals
De Koster and Van Santen
Energetics of Dissociation
on a transition metal such as Fe, Ru

∆Hads (AB)
–150 kJ/mol
Eact
75 kJ/mol

Driving
Force
∆Hads (A+B)
–600 kJ/mol
Trends in chemisorption
Strong atomic adsorption

Cr Mn Fe Co Ni Cu
585 564
Mo Tc Ru Rh Pd Ag
543
W Re Os Ir Pt Au
531 531 N/Metal, kJ/mo

Weaker adsorption

Evac Evac
antibonding antibonding

EF
EF d-band

bonding bonding

s-band

d-metal adsorbed free d-metal adsorbed free

atom atom atom atom

d-band < half filled d-band > half filled

strong bond weaker bond
Dissociation on Different Metals
e.g. Rh and Fe

δEact Rh
∆Hads (AB)

δEact ≈ ½ δ ∆Hads (A+B)

Bronstedt-Polanyi Relation
δ ∆Hads (A+B)
Fe
Trends in chemisorption
easy dissociation

Cr Mn Fe Co Ni Cu

Mo Tc Ru Rh Pd Ag

W Re Os Ir Pt Au

no dissociation

Dissociation on Different Metals

e.g. Rh and Fe

δEact Rh
∆Hads (AB)

δEact ≈ ½ δ ∆Hads (A+B)

Bronstedt-Polanyi Relation
δ ∆Hads (A+B)
Fe
Coordinative unsaturation: higher reactivity

fcc (111) less dense surface

9 neighbours per atom or defects
<9 neighbours per atom
energy

energy
sp - band

Fermi
level d-band

density of states density of states

 Coordinative unsaturation: higher reactivity

fcc (111) less dense surface

9 neighbours per atom or defects
<9 neighbours per atom

energy
energy sp - band

Fermi
level d-band

density of states density of states

Evac
antibonding
antibonding

EF

r ong er
bonding st !
bonding
bond
What is catalysis?
•The potential energy picture
•The kinetic picture
•The chemical bonding picture
If you can explain catalysis along
these three lines you have
a pretty good understanding of
what catalysis on metals means.