CH3010: Catalysis

Air

Prof Adam Lee

leeaf@cardiff.ac.uk
8 lectures

Learning objectives
During this course you should become familiar with:
Experimental reaction kinetics liquid and gas phase reactions
The importance of surface processes.
How surface structure affects the reactivity of materials.
Adsorption processes, physisorption and chemisorption
Adsorption isotherms - Langmuir and BET models.
Kinetics of surface reactions - Eley Rideal and Langmuir Hinshelwood mechanisms.
Surface analytical techniques, including XPS, AES.
Recommended Reading
G.A. Somorjai

Introduction to Surface Chemistry (Wiley)

G.Attard, C.Barnes

Surfaces (Oxford Chemistry Primer)

E.McCash

Surface Chemistry (OUP)

P.W Atkins & J de Paula

Physical Chemistry, 9th Edition Chapter 21

Elements of Phys. Chem., 5th Edition Chapter 1

Tutorial notes on surface chemistry, useful www.chem.qmw.ac.uk/surfaces

2

Why do we care about kinetics?

How fast a process occurs?
- can predict practical/economic feasibility
- can predict risks (heat release, pressure changes)
- alter reactants
- improve reactor engineering
What route is followed?
- what steps are involved (e.g. dissociation, coupling)
- what is the mechanism (how do atoms/molecules interact)
Typical experiments involve:
1. mixing reactants
2. initiating reaction (heat

, light

3. measuring T or P
4. measuring reactant/product concentrations
Crucial that Steps 1-3 >> Step 4
3

Experimental kinetics
Kinetic theory reaction rates:

d [ A]
n
= k [ A]
dt
Theory and experiment linked via the
integrated rate equations

Experimental kinetics concentrations of reactants

Aim of experiment to determine:
Reaction order n
Rate constant(s) k
Activation energy Ea

- steps involved
- intrinsic speed of reaction, bigger = faster
- mechanism
4

Case study: 1
For reactions that occur over minutes or hours, k < 1x10-2 s-1
This measurement timescale is fine for standard undergraduate techniques:
e.g. pH meter

, conductivity

, photometry

Key considerations in choosing a method are the half-life t1/2 and mixing time.

Case study: 1
Consider thermal decomposition of cyclopentene:
T = 500oC 540 oC
t1/4 ~1000 sec

Since pV = nRT
same T

(i.e. p n), and 1 mol of any gas occupies same V at

Measuring p versus time t allows us to track reaction progress

Manometer
Transducer
Reaction vessel in
furnace

Cyclopentene
Vacuum pump

Case study: 1
Consider thermal decomposition of cyclopentene:
T = 500oC 540 oC
t1/4 ~1000 sec
Since pV = nRT (i.e. p n), and 1 mol of any gas occupies same V at same T
Measuring p versus time t allows us to track reaction progress
If all cyclopentene decomposes, pressure x2.

Partial pressure of CP at any time PCP = 2 PCP(t=0) Pt.

8

Analysis
R = 0.9752
Determination of order, n
1. Integrated plots
Plot ln(PCP) vs t and 1/PCP vs t
Ln(CP)

0.018

4.575

0.0135
R = 0.9536

1 / CP

4.8

ln (CP)

Best fit

and compare trend lines via R2 values.

1/CP

4.35

0.009

4.125

0.0045

3.9

(R2

10

15

closest to 1) predicts
order.
Time / min

20

10

15

20

Time /min

BUT
Works best for synthetic data; real data difficult to distinguish.
9

2. Quarter lives method

1st order reactions t1/4 independent of PCP(t=0)
2nd order reactions t1/4 1/PCP(t=0)

examine t1/4 at 3 different values of PCP(t=0) (at fixed T) PCP(t=0) dependence

Can generalise this method to any value of n.
3. Initial rates method
ln(-Rt=0) = ln(k) + n ln(PCP(t=0))
plotting ln(-Ro) vs ln(PCP(t=0)) should be linear with slope = n.
Need to repeat reax. at different T
Initial rates Ro can be obtained from the slope of the tangent at t=0 or more
accurately by fitting a cubic polynomial to the data.

10

 Determination of rate constant

Once we have determined n use appropriate
integrated plot to determine k
Ln(CP)
4.8

ln (CP)

4.6

4.4

4.2

4
0

10

15

20

Time / min

Determination of EActivation
Arrhenius plot of ln(k) vs 1/T slope = -EA/R
Need to repeat reax. at different T
11

Case study: 2
For reactions with t1/2 ~ 1 msec 1 sec we usually use a flow method
Continuous (discharge) flow
Moveable
detector

Mixing
region

Product
(waste)
Reaction region

Very wasteful of reactants and needs moveable detector

12
12

 Stopped flow method

Stopping syringe

Photomultiplier
detector

Light source

Mixing chamber

Reactant syringes

13

Uses much smaller amounts of reactants and employs a fixed detector

e.g. reduction of 2,2 dichlorophenolindophenol (DCIP) by ascorbic acid

DCIP

products

Can use optical absorption detection method: [DCIP ] absorbance

14

Faster reactions (t1/2 < 1 msec) relaxation methods

For example systems at equilibrium

k1

A B
k-1

Monitor time to re-equilibrium system (e.g. [B] or [A]) after perturbation

t* = 1/(k1+k-1)

and

K = k1/k-1

The perturbation should occur in 10-6 10-7 seconds and may b

e:
- pressure jump
- temperature jump
- high electric field pulse
- ultrasonic vibrations
- light pulse (flash photolysis) ultrafast spectroscopy (fs-ps!)
15

 Flash Photolysis very fast reactions (k~50 000 500 000 s-1)
Pre-mixed volume of reactants in a photolysis cell subjected to light pulse producing
atoms, radicals & excited states whose concentration is followed with time.
Advantages:
- no mixing time
- timescales of reax. limited only by
pulse duration (<10-12 s with lasers)
- species formed in the centre of the cell
so can ignore wall reactions.

16

Reaction dynamics
All previous methods consider systems where reactants have a
thermal distribution of energy.
To study elementary reactions ideally want molecules possessing
a specific energy, and only undergoing a single collision.
Solution: Molecular beams

Collimation+rapid expansion make beam:

1. intense
2. linear
3. minimal vibrational excitation
Energy can be tuned:
1. varying T
2. seeding beam with inert elements (e.g. He)
17

Surface chemical processes

$10 trillion!!
35% of global GNP
Surface Chemistry
& Analysis

Electronic
Devices

Heterogeneous
Catalysis
NH3 synthesis
CH3OH synthesis
C2H4 oxidation

Gas sensors (CO)

Tribology

Corrosion
Science

Chemical
Surface
Modification

Optics

Polymer
Science

Medical
Implants

18

Surface Kinetics
Gas phase:
Controlling parameters:

[A], collision rate zAA, collision cross-section A ..

e.g. O2 P = 1 atm; T = 298 K zAA = 2.8 x 109 molecule-1 sec-1

Surfaces:
Rate of gas molecules colliding with surface (flux) = n x c
n = N / V = P / (kT)
;
Rate = P/(2mkT)1/2

Hertz-Knudsen equation
P,V,T

e.g. O2 P = 1 atm; T = 298K rate = 5 x 1023 cm-2 sec-1

Surface chemistry phenomenally fast due to higher collision probability
vast collisional cross-section

19

Surface Terminology
Substrate (adsorbent)
- the solid surface where adsorption occurs

Adsorbate
- the atomic/molecular species adsorbed on the substrate

20

What happens when a molecule collides with a surface?

Nothing - elastic collision, no energy transfer

Atoms/molecules feel attractive potential and stick to

surface - a process termed ADSORPTION
The sticking probability s is defined as:
s = no.of molecules that stick
no. of molecular impacts

0s1

21

Arises from van der Waals forces between a molecule/atom and surface

+ -

Distance from surface

adsorbate

22

Thermodynamics of adsorption
Consider changes in thermodynamic parameters upon adsorption:
3 degrees of freedom S1

Surface

Adsorption
2 degrees of freedom S2

S2 < S1 , S < 0
Recall, G = H - TS

Gibbs-Helmholtz equation

-ve
+ve
Since G <0 for a process to occur spontaneously,
H <0 , i.e adsorption must always be exothermic
23

For dissociative adsorption of molecules, e.g. X2, we need to consider energy:

1. breaking the X-X bond - dissociation energy DXX
2. making 2 new X-M (M=metal atom) bonds - bond strength EX-M
EX-M high
enough

Metal

Metal

Metal
Molecular
adsorption

Dissociation

For the adsorption to be exothermic:

EX-M > DXX/2.

For

N2, EN-M >420 kJ mol-1,

H2, EH-M >200 kJ mol-1

N2 adsorption is more specific.

24

Adsorption types
Chemisorption
H > 50 kJ mol-1
chemical adsorption
chemical bond formation
Confined to single monolayer
Adsorption may be activated
Dissociation possible

EX-M high
enough

Physisorption
H < 50 kJ mol-1
physical adsorption
van der Waals (perm./induced dipoles)
Multilayer adsorption
Unactivated adsorption
Enhanced at low T (Le Chatelier)
Non-dissociative
diffusion
2-D gas

desorption

A2(g) A2(a)
A2(g) 2 A(a)
adsorbed atoms can still
diffuse across surface

simple equilibrium between gas & adsorbed

Surface lifetime, = o e

H/RT

Frenkel eqn.
25

Chemisorption
A true chemical bond forms between the adsorbate and the surface involves electron transfer.

e- transfer
Bonds within the adsorbate molecule are weakened.
fundamental to catalysis!
Chemisorption process may be associative or dissociative.

26

 Hads for dissociative adsorption > non dissociative

Dissociative ads:

O2/W
N2/W
H2/W
H2/Ni

Non-Dissociative

CO/Ni
N2/Ni

Bond dissociation energy of

(Gas Phase)

Hads(kJ/mol)
-600
-340
-160
- 80
-130
- 50

N2 = -950 kJmol-1
H2 = -430 kJmol-1

27

Electronic Properties of Solids

Consider a linear combination of 1s atomic orbitals when going from a
diatomic molecule to an infinite solid

Infinite Solid

]n

]n

]n
28

Band formation
In the solid state bands exist rather than discreet molecular orbitals.
Each band is a continuum of MOs
Consider band structure for Sodium
Atom extended structure
Fermi Energy (EF)

3s1
3s Band

full

2p6

2p Band

Filled

2s2

2s Band

Filled

1s2

1s Band

Filled

29

Fermi energy
Recall from MO theory
N atomic orbitals N molecular orbitals
levels in each band
Each level has space for two electrons.
The Fermi level is the highest occupied energy level in band
structure (equivalent to the HOMO in a molecule).
N.B. For a material to be a conductor, the Fermi level must lie in
a region with unoccupied states above it.
EF
Insulator

Conductor

30

Density of States
Recall:
1. N atomic orbitals N levels in each band
2. Band width increases with orbital overlap
Distribn of energy levels within a band depends on band width
Density of States = No. energy levels per unit
energy in a band
Strong overlap
Broad band
Low Density of States
Weak overlap
Narrow band
High Density of States
31

Partially filled d-band metal

N(E)
Density
of States

Filled d states
Empty d states
sp band

EF
Filled d states

Density
of States

Filled d-band metal

N(E)

sp band
EF
EF

d-orbitals

poor overlap

narrow band
high Density of states

s-orbitals

good overlap

wide band
low Density of states

32

What is the significance of the density of states?

Chemisorption involves electron transfer to/from the surface
Electrons can only be transferred to/from states near the fermi level (Ef).
Direction of e- transfer can be:
Filled states on metal empty orbital on adsorbate
Filled orbital on adsorbate empty state on metal
High DOS at Ef metal has lots of states available for electron transfer
Transition metals (d block) are good catalysts
How do we determine the direction of e- transfer?

Recap:
Combination of atomic orbitals in a extended solid result
band formation
FERMI ENERGY (Ef) = Highest occupied level
DENSITY OF STATES (DoS) = Number of available energy
levels at a particular energy.
DoS at Ef tells us how good/bad solid will be at electron
transfer (e.g.important for electronic interaction with adsorbates
-see later)

The Workfunction ()
Definition
The difference in energy between an electron at rest just outside the
metal surface and an electron at the Fermi Energy.
E>0

Zero Energy Level

E<0

EF

Empty levels

Occupied
States

Fermi Level
Bottom of valence band

E()=W-EF

Electrons are held in a potential well

depends on the depth (W) of the potential well in which the

electrons are held, and the number of electrons.

Intensity0.5

The work function () is measured as the threshold photon energy required

for photoemission
Threshold =

1/
is typically 1-5 eV
is a measure of surface electronic properties and changes in the
presence of adsorbates.

36

Work function changes induced by Chemisorption

Recall chemisorption involves electron transfer
a. Electronegative adsorbates
If the LUMO of the adsorbate < EF then charge is transferred to the
adsorbate.

EF

EF

e-

Metal
1. Ef hence

LUMO

Adsorbate

i.e is +ve

37

b. Electropositive adsorbates
If the HOMO of the adsorbate >EF then charge is transferred to the metal.

EF

EF

1. Ef hence

HOMO

i.e is -ve

38

Examples of work function changes

O/Cu(111)

Positive

H/Mo(111)

Negative

Cs/W(100)

Negative

Cl/W(100)

Positive

39

Recap
WORK FUNCTION () = minimum energy for an electron to be emitted
from the Fermi Level (Ef)
changes in the presence of adsorbates
- Chemisorption
- electronegative adsorbate ALWAYS +ve (e.g. Cl)

- electropositive adsorbate ALWAYS ve (e.g. K)

40

Case Study CO/Pt(111)

varies with fractional coverage ()

Need to consider bonding of CO to surface

41

 Molecular Orbital Diagram for CO (with sp mixing):

6

4
3
Electron configuration: (1)2 (2)2 (3)2 (4)2 (1)4 (5)2 (2)0

42

The 4 orbital is localised on O

The 5 orbital on the C atom
The 2 is anti-bonding

O
1

So what happens at 0.33 ML?

43

Low coverages
Initial adsorption occurs into preferred on-top site

O
C

O
C

5 orbital of CO

2 orbital of CO

Vacant Metal d orbital

Strong
donor

Full metal d orbital

acceptor

donation to metal dominates, hence decreases.

But CO-CO repulsion prevents occupation of every on-top site.
44

Higher coverages
Occupy less favourable bridge sites.

OC

OC

O
C

Weak
donor

acceptor

Charge transfer now dominated by * back-bonding

increases and returns to that of the clean surface

45

 Is there evidence for such adsorption site changes?

Infra-red measurements show:
< 0.33 ML

single band at ~2090 cm-1

linear Pt-C=O species

> 0.33 ML

second band ~1850 cm-1

bridging species

The enthalpy of adsorption (Hads) is also coverage dependent

Hads( kJ/Mol)

- 145

- 96.4

- 48.2

Strong

<0.33

>0.33

0.33

Weak

Coverage (monolayers)

46

Dissociative adsorption NH3 synthesis

Beginning of 20th century, use of nitrogenous fertilisers well established
Principal source NaNO3 (Chile)
Massive demand due to:
population growth
use as explosive
BUT
Sources predicted not to last more than 50 years
Other sources of fixed nitrogen required!
ammonia

Process feeds roughly 33 % of world

47

Haber-Bosch process (1909) commercialised by BASF

Alvin Mittasch tested >4000 catalytic materials in 1000 experiments to
achieve direct combination of H2 and N2
1. Adsorption and dissociation of the reactants
N2(g) N(a) + N(a)
H2(g) H(a) + H(a)

Fritz Haber Carl Bosch

(Nobel Prize, Chemistry
2. Diffusion and reaction of N and H atoms, and desorption1918/1932)
of ammonia.

N(a) NH(a) NH2(a) NH3(a) NH3(g)

The catalyst must get the balance right:
Adsorb N2 and H2 dissociatively
Allow N and H diffusion and reaction
Allow ammonia desorption

48

Potential energy diagram for dissociative adsorption

Transition State
Energy / eV

H+H
Gas phase enthalpy of dissociation
Echem

H2

-Hphysisorption
Distance from Surface (nm)

-Hchem

H
Dissociated state
Fe
H

H
Molecular state

Fe
49

 Activated dissociative chemisorption

Crossover > E = 0
e.g. H2 on Fe
- need to put energy in to system (heat) to dissociate

Non-activated dissociative chemisorption

Crossover E < 0
e.g. CO on Ta
- spontaneous dissociation

50

Molecular vs dissociative adsorption of CO

Dissociated CO

Molecular CO

The catalytic activity of different metal surfaces reflects their interaction with
adsorbates.
Of particular importance is the role of the Fermi level.

51

The position of EF relative to LUMO of the adsorbate affects electron

transfer process (i.e. degree of back-bonding and hence dissociation)
e- transfer

Ti V Cr Mn Fe Co Ni

Carbon
Monoxide

If Ef > LUMO strong back-bonding weakens C-O bond Dissociation

Same principle applies to dissociation of other diatomics e.g. O2, N2, H2
Back-bonding (and hence dissociation) can be tuned by adding dopants
52

How do we measure adsorption?

P1,V1,T

P2,V1,T
P2,V2,T

0,V2,T
Open valve
X

P1 V1 = P2 (V1 + V2) - Kinetic theory of gases

P1,V1,T

P2,V1,T
0,V2,T

P2,V2,T
Open valve

P2 < P2 , due to adsorption of gas molecules onto the surface

By measuring P2 and P2 can calculate number of molecules adsorbed [P2 - P2] 53
Volumetric method

Adsorption isotherms
Plot of number of molecules adsorbed against equilibrium pressure at
constant temperature

Numb
er
molec
ules
adsor
bed, n

A2(g) A2(a)

x
x

[A2(a)] = f (p)

x
x

Mono
la

Surfa

yer

ce

Often use V (volume equivalent at stp)

or (surface coverage) instead of n

Pressure (=P2)

A useful quantity is the monolayer uptake

- the number of molecules which just completely cover the surface.
This can be used to calculate the surface area of a solid

54

Langmuir adsorption isotherm

By making certain assumptions Langmuir derived a simple equation to
describe the adsorption isotherm of any atom/molecule.
Enables us to predict adsorbate coverage ()
calculate reaction rates
optimise reaction conditions (T, pressure)
Based on idea chemical equilibria exist during all reactions:

GAS/LIQUID
reactants, products
solvents

CATALYST
absorbate

- stabilities of adsorbate vs. gas/liquid

- temperature (surface and reaction media)
- pressure (liquid conc.) above catalyst0
55

Equilibrium between gas molecules M, empty surface sites S & adsorbates

e.g. for non-dissociative adsorption

S* + M

S----M

[S*] vacancies
(1- )

[S----M]

[M] gas pressure

adsorbate coverage
P
Products
Reactants

Assumption 1:
Fixed number of identical, localised surface sites

Assumption 2:
Adsorption is immobile no surface diffusion

Assumption 3:
Each adsorption site is occupied by only 1 adsorbate (only monolayer adsorption)
56

Equilibrium constant, b is
b

[Pr oducts]

b =
=
[Re ac tan ts] (1 )P
Rearrange in terms of ,

bP
=
(1 + bP)

Langmuir Adsorption Isotherm

b is Langmuir equilibrium constant ( sticking-probability s )

- depends on Hads
Assumption 4:
Hads and thus b is temperature & pressure independent

57

Tune chemistry

Surface saturated/
poisoned

Self-Assembled
Monolayers

b=10
b=1

b=0.1

Rate of adsorption as b

MoS2Au/(111)
hydrodesulfurisation
catalyst

58

Applying Langmuir adsorption isotherm

bP
=
(1 + bP)
is the fractional surface coverage = n/nmonolayer
b is a constant for specific gas-solid equilibrium.
Rerrange Langmuir isotherm to relate experimental measureables, P and n

P/n = 1/bnm + (1/nmonolayer) P

Plot of P/n vs P should be linear with slope 1/nmonolayer
From nmonolayer, and the cross-sectional area of the adsorbate
calculate surface area of solid.
(often use volume of gas adsorbed at STP instead of number molecules)59

Langmuir analysis of chloroethane adsorption on charcoal

P for gases

V for gases

[C2H5Cl]
(mol/dm13)
0
1.17E103
2.94E103
5.87E103
1.17E102
1.76E102

Mass
adsorbed
(g)
0
3
3.8
4.3
4.7
4.8

[C2H5Cl]/mass

3.90E104
7.74E104
1.37E103
2.49E103
3.67E103

[C2H5Cl]

3.8
2.5
1.3
0
0

[C2H5Cl/]m

Convert moles molecules

0.009

0.0135

0.018

Mass adsorbed m (g)

4.00E-03

Mass of monolayer = 1/slope

= 1/0.198
= 5.05 g

0.0045

y = 0.1982x + 0.0002

3.00E-03

2.00E-03

1.00E-03

0.00E+00
Surface area = molecules x area molecule
0.00E+00

4.50E-03

9.00E-03

[C2H5Cl]

1.35E-02

1.80E-02

60

Langmuir analysis involving two measurements

A carbon sample adsorbs 25 cm3 of nitrogen at a pressure of 10 mbar and 41 cm3 at
a pressure of 18 mbar. Making use of the Langmuir adsorption isotherm, determine
the monolayer capacity of the sample. [R=8.314 J K-1 mol-1]

= 25/Vm at P=10 mbar

= 41/Vm at P=18 mbar

, where Vm is saturation (monolayer) uptake.

and = KP/(1+KP)
Thus 25/Vm = 10K/(1+10K) and 41/Vm = 18K/(1+18K)
Rearranging:

1/K = (10Vm - 250)/25

1/K = (18Vm - 738)/41.
Solve simultaneous equations for 1/K Vm = 205 cm3 (make sure you can do this)
61

Complex adsorption isotherms

Langmuir Isotherm
adsorption stops at the monolayer

During physisorption multilayers form

need a better model to account for this

Multilayer
Monolayer volume
Monolayer

62

SLIME

(matrix protein)

Medical devices
-hip implants
- prosthetics
- scalpels
Fouling
-Bioreactors
- boats
- gum disease

initial irreversible maturation I maturation II dispersion

attachment attachment

BET adsorption isotherm

Brunauer, Emmett and Teller developed more realistic model that:
1. Allows multilayer adsorption
2. Different enthalpy of adsorption of multilayers and monolayers

P
1
(c 1) P
=
+
.
V ( Po P ) Vm c Vm c Po
V = volume of N2 adsorbed
Vm = monolayer volume
P0 = saturation N2 vapour pressure at 77K
P = applied N2 pressure

BET Adsorption
Isotherm
P
= 1 + (c-1) P
n(P - Po) nmc
nmc Po

c accounts for enthalpies of adsorption

c = exp(HDO - HVAPO)/RT
HDO = enthalpy of desorption (strength of adsorbate-surface interaction)
HVAPO = enthalpy of vaporisation (adsorbate-adsorbate interaction in multilayer)64

A plot of P/V(P-Po) vs P/Po should be a straight line

P/V(P-Po)

x
x
x

Gradient = [(c-1)/Vmc],
Intercept = 1/Vmc

solve for c = Gradient / Intercept

(substitute above to find Vm)

P/Po

Vm number of N2 molecules adsorbed,

Area occupied by single N2 molecule is 16.5 2

Total surface area = (no. N2 molecules) x (16.5 x10-20) m2

Isotherm is only valid for P/P0 = 0.05-0.3, outside it is not linear. 65

Example BET calculation

1. Calculate monolayer volume Vm
Intercept = 1/Vmc = 2x10-4
Gradient = (c-1)/ Vmc = 0.014

Gradient = (c-1) x 1/Vmc

= (c-1) x Intercept

Gradient = (c-1) x (2x10-4) = 0.014

(2x10-4)c - (2x10-4) = 0.014
c = (0.014 + (2x10-4))/(2x10-4) c = 71
Intercept = 1/Vmc = 2x10-4
1/(2x10-4)c = Vm
1/((2x10-4)x 71) = Vm Vm = 70.4 cm3
2. Convert Vm to number of N2 molecules
PV = nRT P = 1.01x105 Pa (Nm-2);
V = Vm in m3 (1cm3 = 1x10-6 m3)
R = 8.314 Jmol-1K-1;
T = 298 K (SATP)
1.10x105 x 70.4 x10-6 = n x 8.314 x 298

n = 0.0029 moles

Number N2 molecules = n x NA = 0.0029 x 6.022x1023 = 1.75x1021 N2 molecules

3. Multiply by area of a single N2 molecule
Area of 1 N2 molecule = 16.2 2 = 16.2x10-20 m2
Surface area = 1.75x1021 x 16.2x10-20 = 283 m2

66

Determining the heat of adsorption

For a gas at pressure P in equilibrium with the condensed phase at temperature T.

H ads Clausius-Clapeyron equation

' d ln P $
%
" =
2
dT
RT
&
#
rearranges to:

. P1 +
H ads
ln,, )) =
R
- P2 *

&1 1#
$ !
% T2 T1 "

where Hads = isosteric heat of adsorption (measured at constant )

Measure several adsorption isotherms at different temperatures:
Fractional
surface
coverage

T3

T3 < T2 <T1 ( increases with decreasing T)

T2

For particular read off values for P1, P2, P3

T1

= constant

Plot ln P vs 1/T and slope = -Hads /R

P3 P2

P1

Pressure (=P2)

67

Adsorption summary
All gases Physisorb on any surface when T < condensation temp.
Reactive gas Chemisorb on reactive surface when T>condensation temp.
Langmuir isotherm
- assumes all adsorption sites are identical
- only useful for describing monolayers
BET isotherm
- better model for physisorption
- takes account of varying Hads of mono- and multilayers
- widely applied to surface area analysis
Highly organized macro-mesoporous Al2O3

68

Crystal structures

Face Centred
Cubic (fcc)

Body Centred
Cubic (bcc)

Most common structures for transition metals

69

Miller Indices
Quick way to describe surface:
1. Find the intercepts of the plane with the 3 crystal directions or axes in
terms of primitive vectors (a, b, c)

c
3

= (2, 1, 3)

1
2. Take reciprocals
= (1/2, 1, 1/3)

3. Multiply resulting numbers by the smallest number that yields 3 integers

(h, k, l) notation
i.e. multiply by 6 (h, k, l) = (3, 6, 2)

70

Miller Indices for a simple cubic lattice

(100)

(010)

z
y
(110)

(111)

71

Atom packing in exposed crystal faces

a2

a2
a

(100)

(110)

a3/2
(111)

fcc
(100)

(110)

(111)

bcc
72

Surface energy
In the bulk each atom is surrounded by 12 nearest neighbours STABLE
Consider cleaving a metal crystal to generate a (111) plane

Bulk
12 nearest neighbours

fcc(111)
9 nearest neighbours

Atoms in the surface have lower coordination number

73

Lower coordination number

more unstable/reactive
more bonds broken
higher surface energy

8 nearest neighbours

fcc(100)

6 nearest neighbours
fcc(110)
74

More open faces have higher surface energy i.e. for fcc 111< 100< 110

6 nearest
neighbours

9 nearest
neighbours

8 nearest
neighbours

75

Unimolecular decomposition
Consider the surface decomposition of a molecule A , i.e.

A (g) A (ads) Products

Assumption 4:
Let us assume that :
decomposition occurs uniformly across surface sitesHads is coverage independent
(not restricted to a few special sites)
Assumption 3:

products are weakly bound to surface and, once formed, rapidly

Only 1desorb
adsorbate per site
the rate determining step (rds) is the surface decomposition step
Under these circumstances, the molecules of A on the surface are in
equilibrium with those in the gas phase

predict surface conc. of A from Langmuir isotherm

= b.P / ( 1 + b.P )
76

Rate of surface decomposition (reaction) is given by an equation:

Rate = k
(assuming that the decomposition of Aads occurs in unimolecular elementary reaction step and
that kinetics are 1st order in surface concentration of intermediate Aads)

Substituting for gives us eqn. for rate in terms of gas pressure above surface

Two extreme cases:

Limit 1 : b.P << 1 ;

Rate = k b P / ( 1 + b P )

st order rate constant , k' = k.b

i.e. 1st order reaction (with
respect
to
A)
with
an
1
and
Rate ~ k.b.P
then
( 1 + b.P ) ~ 1

This is low pressure (weak binding) limit:

steady state of reactant v. small

77

 Limit 2 : b.P >> 1 ; then

( 1 + b.P ) ~ b.P

and

Rate ~ k

Rate = k b P / ( 1 + b P )

i.e. zero order reaction (with respect to A)

This is the high pressure (strong binding) limit : steady state surface of reactant ~100%
Rate shows the same pressure variation as

(not surprising since rate !)

78

Bimolecular reactions: 1
Langmuir-Hinshelwood type reaction:

A (g) A (ads)
B (g) B (ads)
A (ads) + B (ads)

AB

AB

(ads)
(g)
rds
fast
Assume that surface reaction between two adsorbed species is the rds.

If both molecules are mobile on the surface and intermix then reaction rate given by following
equation for bimolecular surface combination step:

Rate = k
Since = b.P / ( 1 + b.P ), when A& B are competing for same adsorption sites the relevant
equations are:

79

Competitive Adsorption

Rate

Substituting these into the rate expression gives :

Look at several extreme limits:

Limit 1 :
bA PA << 1

Pure A
&

In this limit A & B are both very low , and

Pure B

bB PB << 1

= b.P / ( 1 + b.P )

Rate k . APA . bBPB = k' . PA. PB

Limit 2 :

[A]/[B]

1st order in both reactants

bA PA << 1 << bB PB

In this limit A 0 , B 1 , and

Rate k . bA PA / (bB PB ) = k' . PA / PB

1st order in A
negative 1st order in B
80

81

Bimolecular reactions: 2
Eley-Rideal type reaction :
Consider same chemistry

A + B AB

A (g) A (ads)

A (ads) + B (gas)

AB (ads)
rds

AB (gas)
fast

last step is direct reax between adsorbed A* and gas-phase B.

where [B] is pressure/conc

in gas or liquid phase

A varied

Rate

Rate = k []

[A ]/ [B]
82

However
Without extra evidence cannot conclude above reaction is Eley-Rideal mechanism
last step may be composite and consist of the following stages

B (g) B (ads)
A (ads) + B (ads)

AB (ads)

slow

AB (g)

fast
fast
with extremely small steady-state coverage of adsorbed B
Langmuir-Hinshelwood
not Eley-Rideal
Test by monitoring rate

vary
vary ratio of

or

pA
pB

over wide range

[A]
[B]

need free sites

83

Example 1
Langmuir-Hinshelwood: CO oxidation over Pt
Highest rate of CO2 production under slightly oxidising conditions:
- a high concentration (~0.75 monolayer) of surface O
- significant no. of Oa vacancies (empty sites)
- CO adsorbs in vacancy with only small energy barrier
O
CO

Calculated energy diagram

CO(g)+O2(g)

CO(g)+O(a)

CO2 (g)

CO(a)+O(a)

Reaction
pathway

84

Example 2
Eley-Rideal: CO oxidation over Ru
Highest rate of CO2 production under oxidizing conditions:
- a high concentration (1 monolayer) of surface O
- no surface CO detectable

O atoms
Ru catalyst

Calculated energy diagram

GAS
CO(g)+O(a)

SURFACE

CO2 (g)

Transition state
85

Inert towards O2

Good for
oxididation

Can adsorb CO

Oscillating reactions of carbon

monoxide oxidation on platinum.

86

Apparatus for Surface Analysis

Ultra High Vacuum Equipment
Measurements require Ultra High Vacuum (< 10-7 torr)
- trajectories of electrons/ions used in analysis remain unperturbed
- surface kept free of contamination

87

Electron analysers
Retarding Field Analyser

88

Concentric hemispherical analyser (CHA)

- ve
+ ve

- ve

89

Elemental analysis of surfaces

X-ray Photoelectron Spectroscopy (XPS)

Kinetic Energy

Typical photon sources:

KE = h - BE
Binding Energy

Mg K = 1254 eV
Al K = 1487 eV
90

XPS spectrum of zirconium

Binding Energy eV
KE of emitted electron varies depending on photon energy

91

Limiting resolution depends on X-ray line width.

- higher resolution achieved using monochromator

92

Monochromated X-rays

Bremsstrahlung background

Can also use synchrotron source

continually variable source of monochromated X-Rays
93

Auger Electron Spectroscopy (AES)

Can use X-ray or electron excitation source
Typical electron excited Auger spectrum

94

The Auger process

Photoelectron
eEAUGER
Ey
Ex
Ep
Ew

Ground
state

Initial
excited
state

Auger
process

Final
state
95

Energy of emitted Auger electron involving levels w, x and y:

Ewxy Ew(Z) - Ex(Z) - Ey(Z)

Internal atomic rearrangement independent of energy source used.
Assign elements in surface using tables of electron binding energy.
e.g. calculate the kinetic energy of the OKLL Auger transition: 493-512 eV
(depending on oxide environment)

96

Surface sensitivity
Why are low energy electron spectroscopies surface sensitive?
- high KE strong scattering by neighbouring atoms
- low KE excitation of

Escape Depth /nm

Universal escape depth curve

Kinetic Energy eV
97

Electrons excited by
backscattering and
emitted

Excitation
source

Auger/photo electrons
excited by incident beam
and directly emitted

Auger/photoelectrons
excited but not lose too
much energy to be emitted

98

Applications
Can use XPS/AES to study thin films/coatings

Frank-Van der Merwe

Stranski-Krastanov

99

Volmer-Weber

Simultaneous Multilayers

100

Id/Io = exp (- d/lcos)

ed

Io = intensity of substrate peak for clean surface

Id = intensity of substrate peak after growth of film
l= escape depth of emitted electron
= angle between surface normal and detector
d = film thickness

101

Angular Resolved XPS

I1 I2

I1 I2
I1/I2
Angle

Fe

I1

Cr

I1
I2

I2

I1/I2
I2
Angle
102

Chemical environment
Electron binding energy shifts depending on atom neighbours
- increases if surrounded by electron withdrawing groups (e.g. O, F)
- decreases

donating groups (e.g. K, Ca, H)

103

Accurate measurement of BE and chemical shift tells us

- surface functionalisation (e.g. polymer coating)
- oxidation state of elements (e.g. rusting)

N 1s XP spectrum of NH3 oxidation catalyst

104

105

Ethene adsorption
C 1s Fast XP spectra of
C2H4 adsorption on Pt(111)
Monolayer

0.20

Precursor-mediated
adsorption

0.15
0.10

Multilayer

0.05
0
0

Exposure / L

di /-bound

C 2H 4
4

Single adsorbate

C2 H
4
C2 H
4

Pt(11
1)

285

284

283

Binding Energy / eV

282

Exposu
re / L

C2H4 / ML

0.25

C 2H 4

2.8
1.23
0.16
0.06

106

Time-resolved XPS
100

Temperature / K

C2H4

C 1s Fast XP spectra of
C2H4 reaction on Pt(111)

200

Ethylidyne
300

H2
400
500

H2

CHx

285 284 283 282

/K

Binding Energy / eV
Carbon
285

284

283

282

Binding Energy / eV

Tem
per
atu
re

Surface coverage = 0.25 ML

126
183
238
293
353
467
621

107

Surface reaction kinetics

di- C2H4

C2H4,H2

0.4

H2

Cgraphite

Carbon

C2H3

0.1
0

3 L C2H4

= 1x1010.0.5 s-1

-9
-10
-11
-12

H2 Desorption

Eact = 57 3 kJmol-1

-8

H2
CHx

0.3
0.2

-7

Total C

ln (Rate)

C : Pt ratio

0.5

C2H4

-13

1st order kinetics

3.5

3.7

3.9

4.1

T-1 / 10-3 K-1

4.3

4.5

Stable ethylidyne intermediate

Eact = 75 kJmol-1
100

200

300

400

500

Temperature / K

650

108

XPS/AES summary
Permit quantitative analysis of surfaces
Sensitive to 0.1-1% monolayer (1012 - 1013 atoms/cm2)
Oxidation state information?
- if oxidation state of element changes electron binding energy changes
chemical shift
- complex for AES as 3 electrons involved, hard to interpret shifts

Surface sensitivity depends on kinetic energy of emitted electron

- 50-500 eV Auger electrons are highly surface sensitive
Auger electron energy independent of energy of excitation source

109

Surface vibrational spectroscopy

RAIRS

Reflection Absorption Infra Red Spectroscopy

110

RAIRS of ethylidyne Pt(111)

1118

2884
Heat
1339

C-H symmetric stretch

C-H deformation

C-C stretch
111

Selection Rules:

Ep

IR

Ep
Es
Surface

Response

Es

Angle of incidence (degrees)

112

Metal Surface Selection Rule

Vibrational mode of surface molecule needs dipole moment perpendicular to
the surface to be detected

113

HREELS

High Resolution Electron Energy Loss Spectroscopy

Sample

Slits

Detector

Monochromator

Electron
Gun

114

Incident electron beam interacts with vibrating molecule

- loses/gains energy
- energy change vibrational frequency

Surface
Specular detection: reflection = incidence

115

Dipole Scattering:

Electric field of e- interacts with dipole to surface

due to molecular vibration.
Strongest in SPECULAR direction

Impact Scattering:

Impact of e- with molecule excites vibration.

Not dependent on orientation of dipole.
Best viewed OFF SPECULAR
116

CO/Ni(111)

CO/Pt(111)

117

HREELS of C2H4

Why do we see the C=C stretch?

118

Summary
Resolution
Pressure Range
Spectral Range

HREELS
> 2meV
< 10-8 torr
> 10 meV

vs

RAIRS
0.1meV
UHV to >1 bar
>100 meV

RAIRS low frequency range is limited by detector, while for HREELS it is

limited by elastic peak width.
Vibrating molecule must have a dipole perpendicular to surface
In HREELS can observe dipoles parallel to surface using impact mode
and working off specular

119

Group frequencies

120

121

Structural characterisation of surfaces

Low Energy Electron Diffraction (LEED)

122

Surface diffraction occurs due to regularly spaced unit cells

Incident electron beam

Diffracted electrons

dsin = n
123

y
L

Sample
dsin = n
and
sin = opposite/hypotenuse = y/L
y/L =

n/d

or

separation of spots 1/d (atom/molecule spacing)

124

LEED pattern for O2/Cu(100)

a
b
Clean Cu(001)
+ 0.25 ML
Oadsorbed

Possible structures of p(2x2) oxygen

unit cell on Cu(100)

125

126

Temperature-programmed desorption

127

C2H3

H2 Desorption

Stepwise
decomposition
3 L C2H4
Quadrupole Mass
Spectrometer

CH3
CH2

100

200

300

400

500

Temperature / K

H2

650
Pt(111)

128

For a simple 1st order desorption the activation energy (Eact) for desorption
can be calculated from the desorption peak temperature using the
Redhead equation:

Eact = RTp [ln(Tp/) - 3.46]

Redhead equation

= heating rate (typically 1-1000 K sec-1)

Tp = peak temperature
= constant (frequency factor) = 1015 sec-1

129

CO/Pt(112)
- stepped surface
- get info about preferential adsorption site
Weakly-bound

Strongly-bound

130

Can also follow surface reactions

Acetophenone decomposition on TiO2(001)

TiO2

Temperature / K

131

Scanning tunnelling microscopy (STM)

Gerd Binnig & Heinrich Rohrer

(Nobel Prize, Physics 1986)

132

At a certain applied potential electrons tunnel to or from tip.

Tunnelling current sensitive to tip sample separation

Sample
S

Vacuum
Level
Fermi
Level

Tip
T

Electronic Wavefunction
Maintain a constant tunnelling current while scanning tip across surface.
Motion of tip towards or away from surface topography of surface.
133

Xenon on nickel (110)

CO on platinum (111)

Fe on Cu(111)

134

Adsorbate-induced reconstruction

N2/Cr(110)

135

Chemical Contrast

Pt/Rh(100)

136

Atomic force microscopy (ATM)

Physical interaction with the surface and tip
Vertical displacement is registered by deflection of laser
Compile a topographic image of surface
Can record images of
- insulating samples
- solid liquid interface
- biological samples

137

138

AFM image of contact lens recorded in saline solution

Hydrophobic lens

Lens with hydrophilic coating

139

Structure sensitivity
Supported metal particle can expose different crystal faces.

In addition there are steps & defects within each particle.

- these are low coordination sites
- region of high potential energy
facilitate bond dissociation

140

Structure Sensitivity occurs when reaction requires specific active sites:

(any mix of step, terrace, kink atoms)

(111)
hex

(100)

square

Stepped surfaces

Stepped + kinked surface

Density of steps and dominant crystal face reflects the metal particle size
changing particle size modifies rate

141

Consider total fraction of available surface sites:

Spherical particles

if Ns = total no. of surface atoms

NT = total atoms in particle
For small particles (< 20)

NS
Dispersion (%) =
x 100
NT

Dispersion 1

if Activity SA, then particle size will rate (per mass of catalyst)
provided exposed surface atom arrangement unchanged

142

Structure sensitive test:

Consider CO + 3H2 CH4 + H2O
Compare specific TON (per surface site)
Ni (100)
9% Ni/Al2O3
5% Ni/Al2O3

If reaction requires specific (4-coord) active site expect

constant Eact

observed

higher rate over surfaces with most (100) sites

larger particles

143

Structure sensitive vs insensitive reaction:

Cyclohexane hydrogenolysis
High step/kink densities high rates
Reaction requires defect sites

-H2

-CHx
contrast with (de)hydrogenation which proceeds over diverse surface arrangements

Reaction kinetics tell us about the active site

144

Summary
The importance of surface processes
How surface structure affects the reactivity of materials
Adsorption processes, physisorption and chemisorption:
- activated vs non-activated adsorption
Adsorption isotherms: Langmuir and BET models
Kinetics of surface reactions:
- Eley Rideal and Langmuir Hinshelwood mechanisms

Surface analytical techniques: specifically XPS/AES

145