Principles of heterogeneous catalysis

About 90% of all industrial processes involve heterogeneous catalysis, the

catalyst being typically a solid while the reactants are in gas or in the liquid
phase. The advantage compared to homogeneous catalysts is that they are
easier to prepare, handle and separate from the reaction mixture.

The catalytic process is run inside a reactor typically operated with

continuous flow under steady-state conditions. The rate is determined,
apart from the nature of the catalytically active surface, by external
parameters like temperature, partial pressures and flow rate.

Usually heterogeneous catalysts consist of fine, often nanosized, powders

supported on nominally inert oxide substrates (Alumina, MgO,...) which
exhibit all possible crystallographic faces.

The catalyst is often a metal to which chemical and structural promoters or

poisons are added to enhance the efficiency and /or the selectivity.
A catalytic reaction is said to be homogeneous if the catalyst is in the
same phase as the reactants.

Examples:

1) the molecule chlorine-tris(triphenylphosphine)-rodium(I)

[RhCl(PPh3)3]
is added to alkene solutions for hydrogenation reactions
(Wilkinson catalyst)

2) Nickel(IV) acetylacetonate (benzene synthesis)

3) Dicarbonyl diiodine-iridium(III) (acetic acid synthesis,
Cativa process)
4) di-cobalt(II) Octacarbonyl (hydroformylation of akenes
to aldehydes)
A catalytic reaction is said to be heterogeneous if the
catalyst is in a different phase than the reactants, e.g.
when the reactants chemisorb on a solid surface.
The weakening of the internal bonds makes the formation
of new bonds with other molecules easier. The product
must have a lower affinity with the catalyst in order to be
released into the gas phase (desorption).
A classical example are the iron powders used in the Haber
process to enable the reaction of H2 and N2 to NH3. The
triple bond between the nitrogen atoms in the N2 molecules
is then broken by dissociative chemisorption.
Other Examples:
1) Pt/Rh (Ostwald process for the production of nitric acid)
2) Titanium tetrachloride and an organometallic composite of Al
(Ziegler- Natta process for polymerization)
3) Chromium oxide for the Phillips process for the polymerization of
ethylene to polyethylene.
4) Zeolite ZSM-5 for hydrocarbon conversion.
 An example of heterogeneous catalysis from everyday life
is the automobile’s catalytic converter transforming
poisonous gases like carbon monoxide and nitrogen oxides,
generated from the combustion of gasoline, into much less
dangerous molecules like carbon dioxide and nitrogen.

Pt/Pd/Rh
2 CO + 2 NO 2 CO2 + N2

The catalyst is composed by a thin metal film of Pt, Pd and

: Rh deposited on a ceramic surface. In this way the amount
of expensive metal is minimized and the active surface
maximized allowing to keep down costs at an affordable
level.
The catalyst causes the dissociative adsorption of NO.
The N atoms recombine to N2 which desorbs. The O
atoms react with adsorbed CO yielding CO2 which
desorbs, too.
Industrial catalysis is still governed by empirical experience.

The single crystal surfaces studied under ultra high vacuum conditions,
necessarily differ from the real catalysis conditions. One speaks in
particular of material and pressure gaps.

The material gap can be bridged by studying the reaction for different
single crystal surfaces including surfaces with well defined defects such
as monoatomic steps or using particles with uniform particle size.

Analysis of the catalyst composition enables the deliberate modification

of the chemical composition studying the way in which the reaction
“digs its own bed”.

The reaction rate is determined by the surface concentration of the

reactants and by barriers to the adsorption which determine the
pressure gap. It can be bridged using lower temperatures to increase the
surface coverage and supersonic molecular beams to study the high
energy tail of the Boltzmann distribution of the reactants
Structure sensitivity arises for H2
dissociation on Fe
 Concept of active site

NO/Ru(0001)
Dissociation barrier for NO = 1,28 eV for the flat terrace
Dissociation barrier at the step = 0.15 eV
Concept of active site
Dissociative adsorption at steps

Ag(210): Oad only No O2 !!!!

(L. Vattuone et al. PRL 90, 228302 (2003))

Ag(410): O2ad + Oad

(L. Savio et al PRL 87, 276101 (2001))

Ion sputtered Ag(100):O2+Oad

(L. Vattuone et al. J. Chem. Phys. 115, 3346 (2001))

Pristine Ag(100): O2 only

13
Poisoning of active sites by Sulphur segregation
 CLASSIFICATION OF REACTION MECHANISMS
→C(gas)+(D(ad) or D(gas))
A(gas)+B(gas)→

Langmuir-Hinshelwood: both reactants are adsorbed at

Langmuir-
the surface and the reaction occurs between surface
species

A(gas)+B(gas)→A(ad)+B(ad)
A(ad)+B(ad)→C ↑ + D(ad) (or D ↑)

Four processes are involved:

adsorption of A and B at the surface
diffusion of A(ad) and B(ad)
reaction between A(ad) and B(ad)
desorption of C

Example: Haber-Bosch synthesis of NH3;

 Rideal: only one reactant has to be adsorbed at the
Eley-Rideal:
Eley-
surface
A(gas)→A(ad)
B(gas)+A(ad)→C ↑ +D (ad) (or D ↑)

Example: H(g) +D/Cu(111)→ HD ↑

H+Dad
HD energy balance: E(HD)=Ediss(HD)+Ekin(H) + Eads(D)=2.3 eV on Cu(111)

This energy is carried away by the products of the reaction which keep memory of
the velocity of the impinging H atoms

On Ni(110), however, also D2 is formed indicating that part of the impinging H

ends up in a translationally hot precursorwhich may transfer its energy to the D
atoms which then react by collision with other D adatoms.
Eley Rideal Mechanism
Eley Rideal Mechanism
 Coadsorption
In the limit in which one can assume that the mutual interaction of the reactants
acts pairwise and independently with interaction energies: εAA , εAB , εBB one has:
If εAA + εBB - 2εAB <0 the two species will repel each other and one has
competitive adsorption
If εAA + εBB - 2εAB >0 the two species will attact each other and one has
cooperative adsorption

Competitive adsorption
may inhibit the sticking
probability of one of
the reactants, which
may be enhanced
adding a promoter
(electropositive atoms
like alkali atoms)
Coadsorption: Ethylidyne plus carbon monoxide on Rh(111)
 Coadsorption O-Ag(110)

O-Ag(110)

Reaction with water to OH

 Poisons and Promoters
Typically electronegative species act as poisons,
electropositive species as promoters

CO methanation on Ni (powders as well as supported clusters). Sulphur

attenuates the catalytic activity of Ni, 10 sites deactivated per S atom

Two possibilities:
1) S blocks 10 sites and the reaction sequence needs for a critical
step of the reaction
2) S has an electronic effect which extends on nearest neighbor
sites

If 1) holds changing the poison has little effect,

if 2) holds a less electronegative adsorbate has a smaller effect
phosphorus is less poisoning than S → electronic effect
Electropositive impurities:
Potassium may accelerate certain steps in a reaction.

CO methanation over Ni occurs by CO dissociation and subsequent

reaction of the carbidic carbon produced with H. The carbidic C coverage
saturates at 50% of a ML. Large H2 pressure needed to find sites where to
dissociate.

The presence of K does not modify the reaction barrier, but

0.1% of K increase the carbon coverage in working conditions from 0.1 ML
to 0.3 ML on Ni(100).

The reaction is poisoned above T=650 K since carbidic carbon coalesces

into unreactive graphite.
 Structural Promoter:

adsorbate which modifies the surface

structure to make it more or less reactive
Modification of the surface structure following adsorption
Adsorbate induce surface restructuring
 Determination of the Reaction Rate
a) power laws
Partial pressure of reactants pi and products pj
r= k pAapBb
useful approach but contains still no information about the progress of the
reaction
b) Attempt to describe the elementary steps: Langmuir approach
The various steps of the reaction are described in terms of rate equations for
adsorption , desorption and surface reaction.
If adsorption and desorption processes are fast then the partial coverages of the
reactants are related to the relative partial pressures through adsorption
isotherms.
This approach may look hopeless given the various structural elements of a real
catalyst. However, it works, and the reason why it works is the same of why
catalysts are robust and can stand a wide range of operative conditions
bA p A bB pB
A ad + Bad  → C
k
Θ A =
1 + bA p A + bB pB
Θ B =
1 + bA p A + bB pB
 bA p A bB pB
A ad + Bad 
→ C k ΘA = ΘB =
1 + bA p A + bB pB 1 + bA p A + bB pB

bAbB p A pB
r = kΘ AΘ B =
(1 + bA p A + bB pB ) 2

For constant T the reaction passes through a maximum since A blocks

the sites for the adsorption of B

c) Microkinetics parameters obtained by DFT calculations of the

elementary steps involved
d) Kinetic Monte Carlo: takes into account the actual neighborhood of the
adsorbed particle detailed insight but heavy computational effort.
 Selectivity

A catalyst may lead to different products which then need to be

separated. The selectivity towards one particular reaction channel is thus
often more valuable than the overall reactivity.

Consecutive reactions A
B
C the reaction passes through a maximum

of B and, if this is the desired product it must then be interrupted at such
point

The reaction has two branches caracterised by reaction rates r1 and r2.
The selectivity is then s1= r1 / (r1 + r2 ) and can be affected by poisoning
one of the pathways
Ostwald process: Ammonia oxidation for the production
of Nitric acid

In industry the catalyst is Pt based and used at T>1000 K

Surface science demostrated that the reaction may

work at T=500 K on RuO2
Mechanism of heterogeneous catalysis
Catalyst consists of Fe3O4 with small concentrations of K, Al, Ca oxides
Surface composition is characterized by the segregation of the additives, which cahnges
further upon reduction.
The catalytically active area consists particles of about 30 nm diameter and a specific
surface area of 20 m2/g exposing metallic Fe covered with a submonolayer of chemisorbed
K and O. Al2O3 and CaO act as structural promoters against thermal sintering
L-H reactions HABER-BOSCH process for NH3 synthesis

N2+3H2 ↔NH3 ; ∆H=-46.1 kJ/mol <0 exothermic process

N2 gas ↔ N2 ad
H2 gas ↔ 2H ad
N2 ad ↔ 2N ad too high energy barrier, rate limiting step
Nad+H ↔ NH ad
NH ad + H ad ↔ NH2 ad
NH2 ad +H ad ↔ NH3 ad
NH3 ad ↔ NH3 ↑

The best catalyst exhibits:

a) the highest dissociative adsorption probability for N2
b) The lowest adsorption energy for atomic N
Optimal choice of the catalyst: Volcano plot
N2 breaks more easily on Mo but the bonding of N with the metal is
then too strong thus poisoning the catalyst.
On Fe and Ru the dissociation reaction is less efficient but N is less
strongly bound and reacts readily with H.
 Specific reactivity for ammonia synthesis
of Fe surfaces 20 atm and 800 K

Active surfaces have

C7 sites !

N2 Sticking coefficient:
Fe(110) 7 x 10-8
Fe(100) 2 x 10-7

Fe(111) 4 x 10-6
Close to the industrial catalyst
Adsorption states of N2/Fe(111)
T<80K physisorption with molecular axis normal to
the surface γ state adsorption energy of 24 kJ/mol
and νNN=2100 cm-1 (for N15 )
T>80K chemisorption with molecules lying side on (π
bonded species) α state adsorption energy
31kJ/mole νNN=1490 cm-1

T> K dissociation νNFe=450 cm-1 β state

surface nitride

sticking probability of N2/Fe(111)

Full line activated indirect adsorption Eact=3kJ/mol
Dashes direct adsorption channel
 Effect of K promoter

N2 Sticking increases to 4 x 10-5

Adsorption energy of α state increases from 31 to 44 kJ/mol

K and O are present in 1:1 ratio on the Fe surface.

They stabilize each other against desorption and reduction.
Since O is electronegative the promotion is effect is reduced but still relevant.
K moreover lowers the adsorption energy of NH3 favouring its desorption
H2 dissociation is easy and not rate limiting.
Since NH3 is the most stable hydrite there is no problem with selectivity
The proposed mechanism allows to calculate the ammonia
production rate up to 300 atm!
Alternative: Mittasch catalyst - alkali promoted Ru
UHV experiment Adsorption on MgO supported Ru at
atmospheric pressure
 CO/Pt(111)

CO forms a c(2x4) layer

occupying both on top and
bridge sites which shift to on
top site in presence of O .
The reaction takes place at
the perimeter of the islands !
Microscopic mechanism of CO-O reaction
CO oxidation on Pt(110)
Adsorbate induced removal of the (1x2) reconstruction
CO oxidation proceeds as well on Pt, Pd and Rh but not on Ru at least in UHV.
The reason is due to the fact that at atmospheric pressure and high T Ru
transforms into RuO2, which is the true catalyst.
Theory: reaction
barrier 0.89 eV
Oxidation of Hydrogen on Platinum
lD in the μm range
D
diffusion length l D =
k3
with k 3 rate constant for OH production
D diffusion coeff.
Numerical simulation of the H2 +O2 reaction on Pt(111)