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

The Concepts of Heterogeneous Catalysis

What is catalysis
The potential energy picture The kinetic picture The chemical bonding picture

P
separation

catalyst

P
catalyst

bonding
A B

reaction

catalyst

potential energy

A A

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

1897 - 1967 Nobel Prize 1956

Cyril Norman Hinshelwood

Irving Langmuir
1881 - 1957 Nobel Prize 1932

Consistent with Sabatiers Principle Coverage dependence: Volcano plot Temperature dependence: Volcano plot

Reaction Mechanism:
A B + + ABads * * Bads

Aads +

! ! " "

Aads Bads ABads + * AB + *

equilibrium; KA equilibrium; KB r.d.s; k fast

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

Reaction rate:

r=

N* k KAKB pA pB (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:

$A =

KA [A] 1 + KA [A]

Rate of reaction, Activation energy, Order of reaction:

r=

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

app a

' ln r 2 ' ln r & %R & RT '(1 / T ) 'T & E

rds a

+ (1 % 2# A ) *H A + (1 % 2# B ) *H B

nA

' ln r & ' ln p A

&

' ln r pA ' pA

& 1 % 2# A

Rate of a Catalytic Reaction: Pressure Dependence

1,2

Eads(A) = Eads(B) = 125 kJ/mol s(B) = s(A) ; Eact = 50 kJ/mol T = 600 K; pB is fixed

rate

normalized rate

1,0 1.0

0.8 0,8
0,6 0.6 0,4 0.4 0,2 0.2

rate

#B

#A #B
0,0 1.0 0,2

#A

#,

0.0 0,0
-1,0 0.1 -0,8 -0,6 -0,4

#*
-0,2

0,4

0,6

0,8

10

reaction order
positive in pA negative in pB

pA/pB

reaction order
negative in pA positive in pB

Rate of a Catalytic Reaction: Temperature Dependence

1,0

Eads (A) Eads (B) s(B) pB Eact

= = = =

135 kJ/mol 125 kJ/mol 10 s(A) pA 50 kJ/mol

normalized rate

0,8 0,6 0,4 0,2 0,0 100

#A

rate

#*

#,

#B
300 500 T (K) 700
reaction order

900

reaction order
negative in pA positive in pB

positive in pA and 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 Mo W

Mn Tc Re

Fe Ru
Os

Co Rh Ir

Ni Pd Pt

Cu Ag 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
anti bonding

atom

much

little overlap

Filling:
bonding

atomic orbital

molecular orbitals

atomic orbital

strong

weak

no bond

and about . . . . .

Bonding in Metals

energy atom metal

4p 4s 3d

sp - band

d-band

density of states

Work Function: Ionization Potential of a Metal

The Surface Contribution to the Work Function
metal surface + + + + + + + ionic cores electrons vacuum

Evac

,
density

EF

distance

: energy barrier for electrons leaving the surface

Strength of metals: Filling of bands EF EF

10

5d-series Cohesive Energy (eV)

8 6

EF
4d-series

4 2 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

3d-series

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
Jellium has no d-band (e.g. Al)

Adsorbed atom

Free atom

Atom on free-electron metals (no d-band):

Evac Evac Evac

EF EF EF

jellium adsorbed free metal atom atom

jellium adsorbed free metal atom atom

jellium adsorbed free metal atom atom

Molecules on free-electron metals (no d-band):

a) Evac -* EF 1s 1s Evac EF 1s -* 1s b)

jellium metal

adsorbed molecule

free molecule

jellium metal

adsorbed molecule

free molecule

Atom on d-metal:
a) Evac
antibonding

b) Evac
antibonding

EF

EF
d-band

bonding s-band

bonding

d-metal

adsorbed atom

free atom

d-metal

adsorbed atom

free atom

Molecular Adsorption on a d-metal

--orbitals Evac -*-orbitals
antibonding

-*
antibonding

EF
bonding

1s

1s

bonding

d-metal

adsorbed molecule

free molecule

CO adsorption on a d-metal
d-5Evac d-2.*
antibonding

2.*
antibonding

EF
bonding

5bonding

d-metal

adsorbed molecule

free molecule

relieved repulsion favors on-top adsorption often called donation

back donation binds molecule to surface weakens internal CO bond! favors multiple coordination

This picture is the key to understanding catalysis in terms of orbital theory

a catalyst breaks bonds...

How?

Atoms prefer high coordination sites

hcp Carbon on Rh(111)
1.99 eV 0.24 eV 0.67 eV

fcc

top

bridge

0.00 eV

hcp Nitrogen on Rh(111)

fcc

top

bridge

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 2.*-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 Mo W

Mn Tc Re

585 564

Fe

Co

Ni Pd
531 543

Cu Ag Au
N/Metal, kJ/mo

Ru
Os

Rh
531

Ir

Pt

Weaker adsorption

Evac
antibonding

Evac
antibonding

EF

EF
d-band

bonding s-band

bonding

d-metal

adsorbed atom

free atom

d-metal

adsorbed atom

free atom

d-band < half filled strong bond

d-band > half filled weaker bond

Dissociation on Different Metals

e.g. Rh and Fe *Hads (AB) /Eact Rh

/Eact 0 / *Hads (A+B)

Bronstedt-Polanyi Relation Fe / *Hads (A+B)

Trends in chemisorption

easy dissociation

Cr Mo W

Mn Tc Re

Fe Ru
Os

Co Rh Ir

Ni Pd Pt

Cu Ag Au

no dissociation

Dissociation on Different Metals

e.g. Rh and Fe *Hads (AB) /Eact Rh

/Eact 0 / *Hads (A+B)

Bronstedt-Polanyi Relation Fe / *Hads (A+B)

Coordinative unsaturation: higher reactivity

fcc (111)
9 neighbours per atom

less dense surface or defects

<9 neighbours per atom

energy

sp - band

Fermi level

d-band

density of states

energy density of states

Coordinative unsaturation: higher reactivity

fcc (111)
9 neighbours per atom

less dense surface or defects

<9 neighbours per atom

energy

sp - band

Fermi level

d-band

density of states

energy density of states

Evac
antibonding antibonding

EF

bonding

bonding

er g n o r st ! 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.