1

Hlne Provendier
Institut de Recherches sur la Catalyse
Universit Claude Bernard Lyon 1
cole FRANCO-VIETNAMIENNE 2005
de CATALYSE
CINETIQUE et RAFFINAGE
Institut de Chimie
Industrielle
Hanoi, 18-22 Avril 2005
2
Physical and chemical techniques
for catalyst characterization
Centre National
de la Recherche
Scientifique
Hanoi, 18-22 Avril 2005
ICI
Dr. Hlne Provendier

Institut de Recherches sur la Catalyse
Villeurbanne
France
Ecole Franco-Vietnamienne 2005 de Catalyse Cintique et Raffinage
3


Part 1 : Adsorption techniques

Part 2 : Diffraction techniques

Part 3 : Spectroscopies


Contents
4
Part 1 :
Characterization of
porous solids
using adsorption
techniques
Part 1 : Adsorption techniques
5
Outline
I. Introduction to solid surface and porosity
1) Porous solids
2) Some definitions
3) Qualitative description of a porous solid
4) Texture of a solid
5) Classification of pores
6) Characterization methods

II. Nature of Adsorption
1) Definition of adsorption
2) Two types of adsorption
3) Transition physisorption-chemisorption
4) Activation energy

III. Physisorption
1) General
2) Theoretical approach
3) Porous volume measurements
4) Pore size distribution

IV. Chemisorption
1) General
2) Chemisorption isotherms

V. Experimental part
6
Most materials are to some extent porous : they contain empty cavities.

Physical properties :
- density,
- thermal conductivity
- strength

The control of porosity is of great industrial importance for example in the design of
catalysts, industrial adsorbents, membranes and ceramics.


Porosity influences :
I. Introduction to solid surface and porosity
In catalysis, porosity determines the accessible surface to the reactant (gas or liquid)
It is thus important to characterize porous solids in catalysis
depend on the pore structure of a solid
the chemical reactivity (activity and
selectivity) of solids
the physical interaction of solids with gases
and liquids
mass and heat transfers in the solid
1) Porous solids
7
Porous solid : a solid with pores, i.e. cavities, channels or interstices,which are deeper
than they are wide.

Pore volume Vp : volume of the pores, as measured by a given method which must be
stated, (together, for instance, with the nature of the probe-molecule, the wavelength of
the radiation used or the ultimate intrusion pressure ...).

Pore size (generally, pore width) : the distance between two opposite walls of the pore
(diameter of cylindrical pores, width of slit-shaped pores).

Porosity c : ratio of the total pore volume Vp to the apparent volume V of the particle or
powder (excluding interparticle voids). c = V
P
/ V

Roughness (or rugosity) factor : ratio of the external surface area to the area of the
geometrical envelope of the particles.

Surface area : extent of the total surface as determined by a given method under stated
conditions. It is essential to state the method used.

2) Some definitions
8
* Closed pores : (a). They influence such
macroscopic properties as bulk density,
mechanical strength and thermal conductivity, but
are inactive in such processes as fluid flow and
adsorption of gases.

* Open pores : (b) (c) (d) (e) and ( f ) . They have
a continuous channel of communication with the
external surface.
- blind (i.e. dead-end, or saccafe) pores : (b) (f)
opened only at one end
- through pores : (e)
opened at two ends


* Classification according to the shape :
- cylindrical (either open (c) or blind ( f ) ) ,
- ink-bottle shaped (b),
- funnel shaped (d) or slit-shaped.
Close to, but different from porosity is the
- roughness of the external surface (g).

Schematic cross-section of a porous solid
3) Qualitative description of a porous solid
f
9
4) Texture of a solid

Texture : detailled geometry of empty spaces in particles. It includes :
- intergranular spaces in agglomerates
- intragranular pore ditribution
- particle shape and external surface
- pore shape and porous volume
- accessibility of gases to internal surface
Parameters describing the texture of a catalyst
- specific surface area (accessible per gram of solid)
- porosity
pore shape
pore size distribution
mean pore size
- granulometry
particle size distribution
shape and size of agglomerates



10
5) Classification of pores

1) By size
- macroporous samples C > 50 nm
- mesoporous samples 2 nm < C < 50 nm
- micro-porous samples C < 2 nm


2) By shape
- cylindrical

- slit-shaped (parallel or not)

- funnel (entonnoir)

- spherical

- ink-bottle shaped

- waved (vague)

11
6) Characterization methods
Specific surface area
Adsorption (BET method)
Porosity
Adsorption (capillary condensation)
Hg porosimetry
Thermoporosimetry
Density measurements
Permeability (for membranes)
Transmission microscopy
Particle size
Sieving
Sedimentation
Light diffusion
X-ray diffraction
Electronic Microscopies (Scanning and Transmission)
12
Solid surfaces show strong affinity towards
gas molecules that it comes in contact with
and some of them are trapped on the surface

the process of trapping or binding of
molecules to the surface is called adsorption

Desorption is removal of these gas
molecules from the surface
2) Two types of adsorption

Physical adsorption :
* Van der Waals forces
* bond energy is less than 50 kJ/mole


Chemical adsorption :
* bond energy is more than 50 kJ /mole
* direct chemical bond

1) Definition of adsorption
Solid
Gas
II. Nature of Adsorption
13
Adsorption and Reaction at Surfaces
14
Rapid equilibration, transport limited
Activated desorption in original form
Exothermic like condensation
-5.
15
Energy similar to chemical reaction
Depends on reactivity of adsorbent and adsorptive
-50..
16
3) Transition physisorption-chemisorption
When P increases, the volume of adsorbed gas Vads increases.
When T increases, the volume of physisorbed or chemisorbed gas globaly decreases.

Physisorption takes place at lower temperature than chemisorption and allows the
molecule to approach the surface without high energy requirement. Physisorption
predominates at low temperature and chemisorption at elevated temperature.
Physisorption
Chemisorption
P = cte
T
Vads
Ex : O
2
adsorption on Ni
At P=1 atm
T = - 200C physisorption
T = 25 C chemisorption
T = 800C oxidation (NiO)
If the molecule is chemically transformed before desorption, there is contact catalysis
17
2) Then chemisorption must be activated to form the transition state (energy required)
Example of H
2
adsorption on Ni catalyst
H
2
+ 2 Ni 2 Ni-H AH
C
= 120 kJ.mol
-1
)
1) Physisorption is the first step of chemisorption
Distance from surface : r (NiH) = 3.2
Distance from surface : r (Ni-H) = 1.6
18
4) Activation energy
E
P
= Energy evolved during
physisorption (exothermic)

E
C
= Energy evolved during
chemisorption (globaly
exothermic)

E
a
= Activation energy
(transition state)

E
d
= Energy required for
desorption
Molecule A-B approaches the surface S of an adsorbent along the distance axis r.
The first interaction process is physisorption at equilibrium position r
P
: exothermic process
E
P
is evolved. Next is the endothermic stage where activation E
a
is input to form the transition
state. This displaces the molecule toward equilibrium position r
C
and E
c
is evolved during
chemisorption. Chemisorption is always an activated process.
19
III. Physisorption
1) General
-Physisorption is not adsorbent or adsorptive specific. This is a process similar to
condensation of gas on a surface.

-The quantity of physisorbed molecules depends on the accessible surface area and not
on its chemical nature.

-Physisorbed molecules progressively form successive layers when the gas pressure P
increases. When P reaches the vapor pressure P
0
, there is condensation on the surface.








-However there can be capillary condensation in the solid pores for P < P
0
depending
on the pore size.
20
For molecules in contact with a solid surface
at a fixed temperature, the Langmuir
Isotherm, developed by Irving Langmuir in
1916, describes the partitioning between gas
phase and adsorbed species as a function of
applied pressure.
The adsorption process between gas phase molecules, A, vacant surface sites, S, and
occupied surface sites, SA, can be represented by the equation,

assuming that there are a fixed number of surface sites present on the surface.

An equilibrium constant, K, can be written :
2) Theoretical approach
a) Langmuir theory (monolayer adsorption)
1) Thermodynamic Derivation

21
Thus it is possible to define the equilibrium constant, b:


Rearranging gives the expression for surface coverage:


u = Fraction of surface sites occupied (0 s u s 1) u = V/Vm
with V = adsorbed volume of gas ; Vm = adsorbed volume at saturation (u = 1)

[SA] is proportional to the surface coverage of adsorbed molecules, or
proportional to u

[S] is proportional to the number of vacant sites, (1 - u)

[A] is proportional to the pressure of gas, P

This simplest theory is based on three assumptions:
1. Adsorption cannot proceed beyond monolayer coverage.
2.All surface sites are equivalent and can accommodate, at most, one adsorbed atom.
3.The ability of a molecule to adsorb at a given site is independent of the occupation of
neighboring sites.
22
2) Kinetic Derivation

The rate of adsorption will be proportional to the pressure of the gas and the number of
vacant sites for adsorption. If the total number of sites on the surface is N, then the rate
of change of the surface coverage due to adsorption is:


The rate of change of the coverage due to the adsorbate leaving the surface (desorption) is
proportional to the number of adsorbed species:

In these equations, k
a
and k
d
are the rate constants for adsorption and desorption
repectively, and p is the pressure of the adsorbate gas.
> 0
< 0
a
d
23
At equilibrium, the coverage is independent of time and thus the adorption and desorption
rates are opposite (equal in absolute value).
where b = k
a
/k
d


The solution to this condition gives us a relation for u:
k
a
P (1 u) = k
d
u This leads to :
I. Langmuir, J. Amer. Chem. Soc., 40, 1361 (1918);
I. Langmuir, J. Amer. Chem. Soc., 54, 2798 (1932);
I. Langmuir, Nobel Lecture, 1932
Ref :
a
d
= -
24
3) Dependence of b on external parameters:

b is only a constant if the enthalpy of adsorption is independent of coverage.

As with all chemical equilibria, the position of equilibrium (determined by the value of b)
will depend upon a number of factors:

1.The relative stabilities of the adsorbed and gas phase species involved.
2.The temperature of the system (gas and surface normally the same).
3.The pressure of the gas above the surface.


In general, factors (2) and (3) exert opposite effects on the concentration of adsorbed
species : the surface coverage may be increased by raising the gas pressure but will be
reduced if the surface temperature is raised.
25
4) Heat of adsorption
b = ka / kd is a T-dependent equilibrium constant

the values of b determined from the Langmuir isotherms at various
temperatures allow for the evaluation of the enthalpy of adsorption,
AH
ads
, through the van't Hoff equation :
b
The temperature dependance of the adsorption isotherm gives the heat of adsorption
26
5) Graphical form of the Langmuir Isotherm

where b
3
> b
2
> b
1

Isotherm is an equation which relates the amt of substance attached to the surface
(or surface coverage u) to its concentration in the gas phase (or gas pressure P) at a
fixed temperature.
For small P values :
u ~ bP

For high P values :
u ~ 1
27
6) Linearisation of Langmuir isotherm
Can be linearised as

1/bV
M

) (P f V =
Graphical determination of b and V
m
bP
bP
V
V
m
+
= =
1
u
m m
V
P
bV V
P
+ =
1
) (P f
V
P
=
28
First theory : Langmuir for monolayer adsorption
Experimental reality : adsorption is higher than monolayer
Second theory : BET for multilayer adsorption
7) Specific surface area determination using Langmuir theory
Some sets of data obtained using nitrogen as the adsorptive gas and adsorbing it at N
2
condensation temperature (77K at 1 bar) plot a straight line only in limited regions, allowing
b and V
m
to be evaluated from the slope (1/V
m
) and the intercept of the line (1/bV
m
).
Slope = 1/V
m
Intercept = 1/bV
m
b = Slope / Intercept
V
m
= 1/ Slope
The specific surface area S
L
of the adsorbent evaluated from Langmuir theory
can be calculated from V
m
by :
0
mV
N V
S
A m
L
o
=
Where :
o is the area of the surface occupied by a single
physisorbed gas molecule (o=16.2 for N
2
)
N
A
the Avogadro constant (N
A
= 6.02 10
23
mol
-1
)
m the mass of the adsorbing solid sample
V
0
the molar volume of the gas (22414 cm
3
)
29
b) Derivation of the BET Isotherm (multilayer adsorption)
BET : Brunauer, Emmet, Teller

Consider a surface:

When the pressure system is increased, the adsorbate adsorbs in multilayers to the surface.
30
Brunauer, Emmet, Teller (BET) theory :

Generalization of the Langmuir theory to multilayers adsorption, with the
following hypotheses :

The evaporation (desorption) rate of adsorbed molecules in a layer is
equal to the condensation (adsorption) rate on the layer under it.

The adsorption heat in the layers (except the first one) is equal to the
liquefaction heat of the gas.

At saturation the number of layers is considered as infinite.

1) Assumptions
31
2) Definition :

u
0
, u
1
, ..., u
n
= Surface area (cm
-2
) covered by 0, 1, ..., n layers of adsorbed
molecules.
At Equilibrium:

u
0
must remain constant. (First layer formation and destruction rates are equal)
Rate of Evaporation from First Layer = Rate of Condensation onto Bare Surface

(Eq.1)
3) Kinetic derivation theory :

For the first layer :
32
Similarly, at equilibrium u
1
must remain constant. (Formation and destruction rates
of monolayer are equal)

k
1
Pu
0
+ k
-2
u
2
= k
2
Pu
1
+ k
-1
u
1

Substituting into (Eq.1) gives for the second layer :

k
-2
u
2
= k
2
Pu
1


Extending this argument to other layers,

first
Monolayer formation :
Monolayer disappearence :
33
Definitions:

Total surface area of the catalyst,
Total volume of gas adsorbed on surface

V
where v
0
is the volume of gas adsorbed on one square centimeter of surface when it is
covered with a complete layer.

where v
m
is the volume of gas adsorbed when the entire surface is covered with a
complete monolayer.

(Eq.2)
34
From Eq.1
with
Assuming that the properties of the 2nd, 3rd ... layers are equivalent, then,

Similarly,

with
u
3
=xu
2
=x
2
u
1

Generally,

u
i
=xu
i-1
=x
i-1
u
1
=x
i-1
yu
0
=cx
i
u
0
with c=x/y
Then
35
Substituting into Eq.2


36
At saturation pressure of gas, P
0
, an infinite number of adsorbate layers must
build up on the surface. From previous equation, for this to be possible, V/V
m

must be infinite. This means that at P
0
, x must equal 1.

So x = P/P
0



This leads to BET isotherm equation
This can be rearranged to give,

(Eq 3)
37
Graphical form of
the BET isotherm
V = f(P)

Replacing x by P/P
0
in Eq 3
4) Graphical form of the BET Isotherm

+
=
0
0
0
) 1 ( 1 ) 1 (
P
P
c P
P
P
c V
V
m
38
5) Dependance of the isotherm form with
the BET constant c
x = P/P
0
E
1
is the adsorption heat of the first layer and E
L
is the liquefaction heat. C is an
indication of the affinity of the adsorbed molecule for the solid : if this affinity is
high, E
1
>> E
L
and c is high

39
From the adsorption isotherms V
M
and c can be deduced by plotting P/(V(P
0
-P)) = f(P/P
0
),
and the experimental results for the slope (generally determined for P/P
0
<0.35) and the
extrapolated value at P=0.

6) Linearisation of BET isotherm
Intercept = 1/cV
M
Slope = (c-1)/cV
M
Intercept Slope
V
M
+
=
1
Slope
Intercept Slope
c
+
=
0 0
) 1 ( 1
) ( P
P
c V
c
c V P P V
P
m m

+ =

BET equation can be linearised as

40
7) Specific surface area determination using BET theory
From V
M
value obtained using BET linearised isotherm, the specific surface area called
S
BET
is calculated using the same formula as in Langmuir theory :
0
mV
N V
S
A m
BET
o
=
Ex : 2 linearised isotherms
BET theory is valuable in the range

0.05 < P/P0 < 0.35

At low P : heterogeneous surface
At high P : capillary condensation
Where :
o is the area of the surface occupied by a single
physisorbed gas molecule (o=16.2 for N
2
)
N
A
the Avogadro constant (N
A
= 6.02 10
23
mol
-1
)
m the mass of the adsorbing solid sample
V
0
the molar volume of the gas (22414 cm
3
)
41
c) Other theories proposed
Depending on the hypotheses made (mono or multilayer adsorption, interactions
between the adsorbed molecules or not), several theories have been developped.
However, the Langmuir and the BET theories are the mostly used.
42
The desorption measurement is performed after adsorption to see if desorption is
exactly the reverse of adsorption or if there is any hysterisis or non-equilibrium
effects in the adsorption/desorption cycle. This is basically performed in reverse of
the adsorption procedure.
Classification following the shape of the adsorption/desporption isotherm
d) Desorption
For mesoporous solids, the adsorbate condenses in the pores at P<P
0
and desorbes from
the pores at P<P<P
0
due to capillary effects. The hysteresis loop is due to capillary pressure,
which retains the condensed gas from desorbing and induces desorption at lower pressure.
Capillary condensation in mesopores
43
Six types of adsorption isotherms following IUPAC classification :
Type I : non porous or micro-porous samples (C < 2 nm)
Types II and III : macroporous samples (C > 50 nm)
Types IV and V : mesoporous samples (2 nm < C < 50 nm)
Type VI : step isotherm (rare)

Types III and V correspond to a low enthalpy of adsorption (exponential)

e) Types of isotherms
Ref : K.S.W. Sing et al., Pure and Appl. Chem., 57, 603, 1985
44
* Nitrogen (at 77 K) is the recommended adsorptive for determining the surface area and
mesopore size distribution, but it is necessary to employ a range of probe molecules to obtain
a reliable assessment of the micropore size distribution.

* An alternative technique to gas adsorption (e.g. mercury porosimetry) must be used for
macropore size analysis.

* Krypton adsorption (at 77 K) is usually adopted for the determination of relatively low
specific surface areas (< 2 mg
-l
), but this technique cannot be employed for the study of
porosity.
f) Choice of adsorptive :
Depending on the adsorptive and on temperature and pressure, the area of surface occupied by
one molecule (o) varies. A rough mean value derived from assumption of close packing at the
surface is given by :



3 / 2
2 / 1
) 2 ( * 4
* 866 . 0 * 4

=
p
o
A
N
M
With M the molecular weight
And p the density of liquid adsorbate
Ex:

N
2
o = 16.2
Ar o = 14.2
Kr o = 21.0
45
3) Porous volume measurements
a) Density measurements using Hg-He volumetry
The pore volume (Vp) is the total volume of the pores of 1g of solid. It results from the difference
between the apparent volume (Va) of 1g of solid and the real volume (Vr) occupied by the
molecules contained in 1g of solid.
Vp = Va Vr = (1/p
a
1/p
r
)
cm
3
.g
-1
With p
a
the apparent density
And p
r
the real density
1) He expansion in a closed chamber of volume V (cm
3
) containing a mass W (g) of solid
He occupies the intergranular volume (Vg) and penetrates in the pores (Vp) but doesnt adsorb.
The real density is given by :
) (
P g
r
V V V
W
+
= p
2) Hg filling. After He evacuation, the chamber is filled with Hg at 1 atm.
Hg occupies the intergranular volume (Vg) but doesnt penetrate in the pores at 1 atm.
The apparent density is given by :
g
a
V V
W

= p
46
4) Pore size distribution
a) Capillary condensation methods
1) Kelvins law

This law considers only the capillary condensation phenomenon (0.35 < P/P
0
< 0.95).
A gas condensation on the surface of a cylindrical pore follows the law

is the superficial tension of the liquid adsorbate, r
K
is the pore radius (meniscus),
P is the gas pressure and P
0
the saturation pressure of the gas,
V
M
is the molar volume of the condensed adsorptive and u is the wetting angle.
If the liquid perfectly wets the surface cosu =1.


Hence at a given P
1
there is a pore radius r
1
such that all the pores with r < r
1
are filled
and all the pores with r > r
1
are empty.

u

cos
2
ln
0
RT r
V
P
P
K
M
=
|
|
.
|

\
|
However, due to different meniscus shapes during adsorption and desorption,
the pressure for emptying the pore is lower than condensation pressure, which
explains the hysteresis loop on isotherms of mesoporous solids.
47

2) Barrett, Joyner and Halenda (BJH) model

This model completes the Kelvin approach by considering also the variation of the number of
adsorbed layers. After evaporation of condensed liquid, adsorbed molecules remain as a film.

The pore radius r is the sum of the Kelvin radius r
K
plus the multilayer thickness t of the
adsorbed molecules forming a condensed film:
r = t + r
K

The law t = f(P/P
0
) was the object of many studies, but generally the law used for N
2
is the
following Hasley equation :



3 / 1
0
ln
5
54 . 3 ) (

|
|
.
|

\
|
=
P
P
nm t
Ref : G.D. Hasley, J. Chem. Phys., 16, 931 (1948)
t
r
K
r
Cylindrical pore
filled with a film (t)
of condensed liquid
From an elementary variation of P (dP), the elementary pore radius (dr) and the elementary
pore volume (dV
P
) are calculated. The pore size distribution is given by (dVp/dr) = f(r)
48
However, the shape of the pore is not always cylindrical and the shape of the hysteresis
loop on the isotherms gives some information about the shape of the pores.

Isotherms are classified following their shape by J.H. de Boer
Ref : J.H. De Boer, The structure and Properties of Porous Materials, D.H. Everett et F.S. Stone Ed.,
London, (1958) 68
3) Influence of the pore shape
49
4) Hg porosimetry
A non-wetting liquid (t/2 < u < t) requires a positive excess hydrostatic pressure AP to be applied
to enable it to enter pores of radius r ; AP will vary inversely with r.

This principle is the basis of mercury porosimetry :
A weighed sample is enclosed in a stout metal bomb, and evacuated to remove air from the pores.
Mercury is then admitted to fill the cell and surround the sample, and is subjected to progressively
increasing pressures, applied hydraulically.
At each pressure P, the corresponding volume V
of mercury contained in the cell is measured.
It is assumed that as the pressure is
increased, mercury enters pores in
decreasing order of size. Thus, if AV is the
volume intruded between P and P+ AP, it
will equal the volume of pores with radii
between r and r - Ar, with





In this way, a volumetric distribution of
pore sizes is obtained (dV/dr = f(r)).
P
r
u cos 2
=
: superficial tension of Hg (484 mN.m
-1
)
u : contact angle (141)
50
Example of pore size distribution
P/P
0
Vads
Treatment of mercury intrusion data
Nitrogen adsorption-desorption
isotherm and corresponding
pore size distribution
51
IV. Chemisorption
1) General
Very exothermic (heat of adsorption up to 500 kJ/mol)

There is creation of a chemical bond between adsorptive and adsorbent
(electron transfert)

Activated phenomenon
(Ea required)





Chemisorption can be dissociative :
H
2
+ 2 Pt 2 Pt-H

H
2
+ ZnO
-Zn-H
-O-H
Ea
Ed
AH
52
2) Chemisorption isotherms
a) Langmuir theory
Assumptions :

The surface of the solid contains a fixed number (Ns) of chemisorption sites
Only one adsorptive molecule at a time can occupy a site
The heats of adsorption of each site are supposed equal and independant of the coverage u
There is no interaction between adsorbed molecules
Similarly to the equation obtained for physisorption, the fraction u of the sites
which are occupied is given by Langmuir equation
With : N = number of sites currently occupied
Ns = total number of accessible sites
b = coefficient depending on AH and T
Va = chemisorbed volume
Vm = volume of chemisorbed monolayer
bP
bP
V
V
N
N
m
a
s
+
= = =
1
u
Vm is obtained for u = 1 (all accessible chemisorption sites are occupied)
53
b) Real isotherm
As seen before, chemisorption may yield Type I (Langmuir) adsorption isotherm :
However in practice, a true Type I isotherm is rarely
obtained since Va usually continues to increase as P
increases after saturation of the active sites.

This method involves a combination of
physisorption (reversible) and chemisorption
(irreversible)
To differenciate the chemisorption from
the physisorption contribution, the sample
is evacuated after a first saturation, which
removes only the physisorbed gas.

Then the analysis is repeated but this time
the sample is already saturated with
chemisorbed molecules : only
physisorption is measured.

The difference A-B
corresponds to chemisorption
and follows Langmuir model.

54
c) Number of accessible active sites (Ns)
From the Langmuir equation :
Vm is obtained by plotting (P/Va) = f(P)
Ns could be obtained by plotting (P/N) = f(P)

bP
bP
V
V
N
N
m
a
s
+
= = =
1
u
Knowing :
the monolayer volume of chemisorbed molecules (Vm)
the stoichiometric factor Fs (number of surface atoms interacting with one adsorptive molecule)
The number of accessible active sites Ns is obtained by :
0
V
F N V
N
s A m
s
=
With N
A
= Avogadros number
V
0
= molar volume of adsorptive
Fs depends on the adsorptive and on the adsorbent ; it can often be found in literature
Ex : For H
2
Fs = 2 on Co, Ni, Pt
For CO Fs = 1,15 on Ni
Ni=CO
and
Ni
Ni
CO
(mean value)
because are formed
Fs = 2
Fs = 1
55
d) Metal dispersion
Usual catalysts are composed of an active metal deposited on an oxide (inactive) support.
The total amount of active metals added to the support is known from the preparation method.

Due to high calcination (or pretreatment or reaction) temperatures, some of the active metal may
become inaccessible to or inactyive toward the reactant molecules due to migration into the support
bulk, formation of a new product, sintering toward formation of larger particles
All these processes lead to a decrease in the active surface area.

It is extremely important for catalysis to determine the accessible quantity of active species since it is
related directly to the overall performance of the catalyst and the efficiency of the activation procedure.

The fraction of the total active metal sites (N
T
) which are accessible to the reactant is called dispersion.
Dispersion D is given as
a percentage :
100 * (%)
T
S
N
N
D =
56
V. Experimental part
1) Experimental procedure
a) Sample preparation
The sample should be finely crushed (higher specific surface area) and degased in order
to evacuate the gases initially adsorbed on the sample. This surface cleaning (degassing)
is most often carried out by placing (about 50 mg) of the solid in a glass cell and heating
it to 350C (at least 3h) under vacuum or flowing inert gas.

If this degassing is performed on another apparatus than the adsorption measurements,
the sample should be kept under vacuum in a special cell until adsorption measurements.
The quantification of the adsorbed gas can be performed using various techniques :
Gravimetry
Volumetry
Gas Chromatography
Thermic conductivity
b) Adsorptive analysis
57
2) Apparatus used for adsorption
a) Scheme
58
b) Picture
Once clean, the sample is brought to a constant temperature by
means of an external bath. Then adsorptive pressure is slowly
increased and adsorption takes place.
59
In conclusion :

-physisorption is performed mainly with N
2
at 77K (Tcondensation at 1atm)

determination of specific surface area S (support and metal) accessible
to the gas reactant.

Supports with high S values permit to prepare catalysts with higher metallic
dispersion




-chemisorption is performed with a suitable gas (H
2
, CO) at higher temperature
(around room temperature) depending on the affinity of the gas for the metal
and of the dissociation stoechiometry (Fs). Chemisorption takes place on metal

determination of the number of active metallic sites (and dispersion)
High metallic dispersion permits higher activity of the catalyst



60
1. S. Brunauer, "Physical Adsorption" (Princeton University Press, Princeton, N. J., 1945)
2. P. Atkins, "Physical Chemistry" (Freeman, New York, 1978)
3. G. A. Somorjai, "Principles of Surface Chemistry (Prentice-Hall, Englewood Cliffs, N. J. 1972)
4. R.S. Drago, C.E. Webster, and J.M. McGilvray, J. Am. Chem. Soc., 1998, 120, 538
5. Nelson FM and FT Eggertsen : Determination of surface area, Adsorption measurements by a continuous
flow method. Anal Chem, 30:1387-1958.
6. Qadeer R, S Akhtar, J Hanif and A Majeed : Nitrogen adsorption on La
2
O
3
(La=Pr, Nd, Gd, Dy, Er)
powder by continuous flow method. Sci Intl (LHR), 6:215-217, 1994.
7. Brunauer S, LS Dening, WS Dening and E Teller : On a theory of the van der Waals adsorption of gases.
J Am Chem Soc, 62:1723-1732, 1940.
8. Qadeer R, J Hanif, M Saleem and M Afzal : Characterization of activated charcoal. J Chem Soc Pak,
16:229-235, 1994.
9. Stoeckli HF, JP Houriet, A Perret and U Huber : In Characterization of Porous Solids, Eds SJ Gregg,
KSW Sing, HF Stoeckli, London Society of Chemical Industry, P 31, 1978.

References


61
Part 2 : Diffraction techniques
X-Ray Diffraction
62
Outline
I. Basics in crystallography
1) Nature of solids
2) Crystal structures
3) Bravais space lattice
4) Indexing of planes and directions

II. X-Ray Diffraction (XRD)
1) What are X-rays?
2) Production of X-rays
3) Principle of X-ray diffraction by a particle
4) Principle of X-ray diffraction by solids (crystals)
5) Reciprocal lattice
6) Diffraction pattern
7) Ewald construction

III. Methods used to obtain a XRD pattern
1) Rotating Crystal Method
2) The Laue Method
3) The Powder Method

IV. Experimental part
1) Apparatus
2) Preparation of the sample
3) Standard acquisition
4) Determination of crystalline phases
5) Determination of mean crystal size

V. Applications of XRD
63
I. Basics in crystallography

1) Nature of solids
Solids can be described as :

amorphous : the atoms are arranged
in a random way similar to
The disorder we find in a liquid
Ex : glasses are amorphous materials


crystalline : the atoms are arranged in a regular pattern
There is as smallest volume element, called unit cell,
that by repetition in three dimensions describes the crystal

The unit cell is described by - three axes (base vectors) a, b and c
- three angles o, | and ;
Ex : quartz, NaCl, perovskites
About 95% of the solids can be described as crystalline
Quartz crystal
64
2) Crystal structures

7 crystal structures (primitive cell)
Examples of Bravais lattice
for cubic structures
Addition of atoms
14 Bravais space lattice
65
http://epswww.unm.edu/xrd/symmetry.pdf
3) Bravais space lattice
14 Bravais space lattice


P - Primitive: simple unit cell
F - Face-centered: additional point
in the center of each face
I - Body-centered: additional point
in the center of the cell
C - Centered: additional point in
the center of each end
R - Rhombohedral: Hexagonal
class only

66
14 Bravais space lattice
Cubic
Tetragonal
Hexagonal
Orthorhombic
Monoclinic Triclinic
http://www.uwgb.edu/dutchs/symmetry/bravais.htm
P
Rhombohedral
67
In the lattice of a crystal, there are many
different planes with different spacings.
The interplanar distance d(hkl) is the minimal
spacing between two consecutive planes of
the same family (hkl).
The plane (hkl) is indexed
using the coordinates of
the vector starting at point
(ooo) and ending at point
(hkl), which is in direction
[hkl] and perpendicular to
the plane (hkl).
4)
h, k, l are called Miller indexes
68
5) Aims of XRD characterization of catalysts
Heterogeneous catalysts are often composed of one of several metals
deposited on a support (oxide) like Ni / Al
2
O
3
or Ni-Rh / Al
2
O
3
(reforming catalysts)

The amount of each element is known from elemental analysis, but the
crystalline structures formed during preparation must be known in order
to understand the activity of the catalyst.

For example, the same elements could create other phases like spinels NiAl
2
O
4
,
much less active in reforming catalysis than metallic Ni. If we do not know that Ni is
inserted in a spinel structure, we could conclude that Ni is a bad active phase.

It is also important to know the environement of the Ni in Ni-Rh / Al
2
O
3
catalyst :
Question of Ni-Rh alloy formation or not? What is the active phase?


The crystalline structure of the catalyst is important because it influences
the catalytic activity.



69
II. X-Ray Diffraction (XRD)

X-rays are electromagnetic radiation (like light rays) but with much higher
frequency and thus a much higher energy and much lower wavelength

Wavelength : 0.02 < < 0.2 nm
Energy : E = h.c /
X-rays were discovered in
1895 by Rntgen
1) What are X-rays?
70
2) Production of X-rays
X-rays are emitted
when electrons
from L layer
relax to K layer
71
3) Principle of X-ray diffraction by a particle

An electron in an alternating electromagnetic field will oscillate with the same
frequency as the field.

When an X-ray beam hits an atom, the electrons around the atom start to oscillate
with the same frequency as the incoming beam. The particle scatters the incident
beam uniformly in all directions.

72
In a solid, in almost all directions there will be destructive interference,
that is, the incoming waves are out of phase and there is no resultant energy
leaving the solid sample.

However the atoms in a crystal are arranged in a regular pattern, and in a few
directions there will be constructive interference. The waves will be in phase
and there will be well defined X-ray beams composed of a large number of
scattered rays mutually reinforcing one another.
4) Principle of X-ray diffraction by solids (crystals)
a) Introduction
73
Consider first a single plane of
regularly spaced atoms:
Imagine a beam of coherent light is
incident on the atoms at an angle
u
IN.
Some of the rays interact with the
atoms and are scattered in all
directions. (Most of the rays are
transmitted.)
Consider the two scattered waves, A and B. They are in phase, reinforcing each
other to give a diffracted beam, only when they travel the same distance, i.e.
when x = y. This only occurs for scattered waves with an outgoing angle of
:

u
OUT =
u
IN
Thus a diffracted beam from a single row of atoms is made up of all the waves
which are scattered with an outgoing angle equal to the incoming angle of the
incident waves. This is true for incident waves of any wavelength.

b) Diffraction by a single layer of atoms
74
Consider many layers of regularly
spaced atoms, such as it might be
encountered in a crystalline material
It is interesting to know what spacing of the layers of atoms will give rise to
scattered waves being in phase, when interacting with many layers of atoms.

Consider two waves C and D, scattered from particles in adjacent planes
separated by a distance d. They are only in phase if the extra path length of
wave D over C (= x + y) equals a whole number of wavelengths.

The equation for this path difference gives the Bragg law:
x + y = 2dsin
u
= n

c) Diffraction by many layers of atoms
75
Braggs law
76
Consider a beam of waves to be incident on a crystal.
The measurement, r, made from the diffraction pattern,
tells us about 2
u
B. From this we can deduce 1/d, since
we know that for diffraction of radiation of wavelength,

, the Bragg angle,

u
B, increases with 1/d.
6) Diffraction pattern
77
The relation by which diffraction occurs is known as the
Bragg law or equation.



Because each crystalline material has a characteristic atomic
structure, it will diffract X-rays in a unique characteristic
pattern.
Possible characterization of crystals
and crystalline phases in solid catalyst
using X-ray diffraction
n. = 2 d
(hkl)
sin u
78
Diffraction can occur whenever Braggs law is satisfied. With
monochromatic radiation, an arbitrary setting of a single crystal in an x-ray
beam will not generally produce any diffracted beams. There would
therefore be very little information in a single crystal diffraction pattern
from using monochromatic radiation.

This problem can be overcome by continuously varying

or
u
over a
range of values, to satisfy Bragg's law. Practically this is done by:
using a range of x-ray wavelengths (i.e. white radiation), or
by rotating the crystal or, using a powder or polycrystalline
specimen.
3 methods
Rotating crystal method
Laue method
Powder method

III. Methods used to obtain a XRD pattern
79
In the rotating crystal method, a single
crystal is mounted with an axis normal
to a monochromatic x-ray beam. A
cylindrical film is placed around it and
the crystal is rotated about the chosen
axis.

As the crystal rotates, sets of lattice
planes will at some point make the
correct Bragg angle for the
monochromatic incident beam, and at
that point a diffracted beam will be
formed.

The reflected beams are located on the
surface of imaginary cones. When the
film is laid out flat, the diffraction spots
lie on horizontal lines.

1) Rotating Crystal Method
80
2) The Laue Method
The Laue method is mainly used to determine the orientation of large
single crystals. White radiation is reflected from, or transmitted through,
a fixed crystal.

The diffracted beams form arrays of spots, that lie on curves on the film.
The Bragg angle is fixed for every set of planes in the crystal.

Each set of planes picks out and diffracts the particular wavelength from
the white radiation that satisfies the Bragg law for the values of d and
u

involved. Each curve therefore corresponds to a different wavelength.

The spots lying on any one curve are reflections from planes belonging to
one zone. Laue reflections from planes of the same zone all lie on the
surface of an imaginary cone whose axis is the zone axis.

81
Back-reflection Laue

In the back-reflection method, the film is
placed between the x-ray source and the
crystal. The beams which are diffracted in a
backward direction are recorded.
One side of the cone of Laue reflections is
defined by the transmitted beam. The film
intersects the cone, with the diffraction
spots generally lying on an hyperbola.

Transmission Laue

In the transmission Laue method, the film is
placed behind the crystal to record beams
which are transmitted through the crystal.
One side of the cone of Laue reflections is
defined by the transmitted beam. The film
intersects the cone, with the diffraction spots
generally lying on an ellipse.

82
Crystal orientation is determined from the position of the spots. Each spot
can be indexed, i.e. attributed to a particular plane, using special charts.
The Greninger chart is used for back-reflection patterns and the Leonhardt
chart for transmission patterns.


The Laue technique can also be used to assess crystal perfection from the
size and shape of the spots. If the crystal has been bent or twisted in
anyway, the spots become distorted and smeared out.

83
The powder method is used to determine the value of the lattice parameters
accurately. Lattice parameters are the magnitudes of the unit vectors a, b and c
which define the unit cell for the crystal.
3) The Powder Method
If a monochromatic x-ray beam is
directed at a single crystal, then only one
or two diffracted beams may result.
If the sample consists of some tens of
randomly orientated single crystals, the
diffracted beams are seen to lie on the
surface of several cones. The cones may
emerge in all directions, forwards and
backwards.
A sample of some hundreds of crystals (i.e. a powdered sample) show that the
diffracted beams form continuous cones.
A circle of film is used to record the diffraction pattern as shown. Each cone intersects
the film giving diffraction lines. The lines are seen as arcs on the film.

84
Example : powder diagram of MgO (cubic centerd faces) obtained with Cu-Ko
in a Debye-Scherrer chamber of 180 nm (fotographic film)
2S=4ru
85
IV. Experimental part
1) Apparatus
A XRD apparatus is basically composed of three parts :

- the X-ray source

- the sample

- the detector
fixed in a fotographic chamber
located on a goniometer
a) General
86
b) Source of X-rays :
- X-ray tube
high speed e- are slown down by an anode and emit X-rays
(not polarised)
- synchrotron
production of e- with parallel spins (polarised X-rays)
87
X-rays are electromagnetic radiation similar to light, but with a much
shorter wavelength.

They are produced when electrically charged particles of sufficient
energy are decelerated. In an X-ray tube, the high voltage maintained
across the electrodes draws electrons toward a metal target (the anode).

X-rays are produced at the point of impact, and radiate in all
directions.

Tubes with copper targets, which produce their strongest characteristic
radiation (Ko1) at a wavelength of about 1.5 angstroms, are commonly
used for geological or solid state chemistry applications.



88
c) X-ray detectors

Qualitative detectors : fluorescent screen or fotographic film
Quantitative detectors :
1. Gas ionisation detectors
2. Solid detectors (scintillation counter, semi-conductor detector)





scintillation counter
semi-conductor detector
89
d) Sample part
The simpliest apparatus is a fotographic chamber.
Debye-Scherrer chamber Guinier chamber
Polycrystalline sample
Monocrystal sample
1) Fotographic chambers
X-ray source
Sample
Diffraction cone
Fotographic
film
Collimator
X-ray
source
Crystal
Sample
90
The apparatus which is nowadays the mostly used is the powder
diffractometer with Bragg-Brentano focuser.

The basic geometry of an X-Ray Diffractometer involves a source of
monochromatic radiation and an X-ray detector situated on the
circumference of a graduated circle centered on the powder specimen.

Divergent slits, located between the X-ray source and the specimen, and
divergent slits, located between the specimen and the detector, limit
scattered (non-diffracted) radiation, reduce background noise, and
collimate the radiation.

The detector and specimen holder are mechanically coupled with a
goniometer so that a rotation of the detector through 2u degrees occurs
in conjunction with the rotation of the specimen through u degrees, a
fixed 2:1 ratio.

2) X-Ray Powder Diffractometer
91
92
Diffractometer D8-advance
Bruker
93
A curved-crystal monochromator containing a graphite crystal is normally used to
ensure that the detected radiation is monochromatic.

When positioned properly just in front of the detector, only the Ko radiation is
directed into the detector, and the K radiation, because it is diffracted at a slightly
different angle, is directed away.

The signals from the detector are filtered by pulse-height analysis, scaled to
measurable proportions, and sent to a linear ratemeter for conversion into a
continuous current. Common output devices include strip-chart recorders, printers,
and computer monitors.

94
2) Preparation of the sample

The sample is ground into fine powder and deposited on a glass support
Few drops of ethanol are spread above the powder and mixed to obtain a
homogeneous suspension.
Ethanol evaporates rapidly and the powder is then well spacially distributed
on the support.

A varnish can be used to protect the sample from oxidation or the sample
can be placed under an inert atmosphere in a chamber equipped with X-ray
transparent windows.
3) Standard acquisition

Continuous scanning with 2u variation
from 10 to 90 with 1s step every 0.02
95
Examples of diffractogram obtained by powder method
96
4) Determination of crystalline phases
Comparison of the diffractogram of the sample with those of JCPDS
(Joint Comittee on Powder Diffraction Standards) Databank.
97
5) Determination of mean crystal size

Width of the peaks varies inversely
proportional to cristal size

High crystral syze lead to very fine
diffraction peaks
98
Diffraction patterns can be used in order to :

Identify the crystalline compounds and their phases in a powder by
refinement of the complete XRD pattern according to Rietveld
(comparison with JCPDS files containing lots of compounds diffraction
patterns)

Measure the average spacing between layers or rows of atoms

Determine the precise crystallographic lattice constants in particular for solid
solutions (incorporation of atomic species into a host lattice)

Determine the orientation of a single crystal or grain

Find the crystal structure of an unknown material

Measure the size, shape and internal stress of small crystalline regions, degree
of cristallinity of rapid solified materials
V. Applications of XRD
99
Examples of XRD applied to catalyst characterization
1) Preferential orientation
Polycrystalline gold film
with statistical orientation
Mica muscovite with
preferential
orientation of the
cystals in (00l)
direction
100
2) Resolution between two phases
Profile analysis showing
the resolution of the
tetragonal and
monoclinic phases in a
Zr(Y)O
2
ceramic
101
0
2000
4000
6000
8000
10000
20 30 40 50 60 70 80 90
I
n
t
e
n
s
i
t

*
*
*
* *
*
*
*
* *
*
*
*
*
*
a
b
2u
* LaFeO
3
(f. JCPDS 37-1493)
Example of perovskite solid solution LaNi
x
Fe
1-x
O
3
XRD of 2 perovskite catalysts : LaNi
0,3
Fe
0,7
O
3
(a) et de LaNi
0,7
Fe
0,3
O
3
(b)
Formation of a unic perovskite structure
3) Solid solution
Ref : H. Provendier et al., Applied Catalysis I, 180 (1999) 163-173
102
0
500
1000
1500
2000
2500
3000
3500
4000
32 32,2 32,4 32,6 32,8 33 33,2 33,4
I
n
t
e
n
s
i
t

a
b
* LaFeO
3
(f. JCPDS 37-1493)
LaNiO
3
(f. JCPDS 33-0711)
2u
Zoom into the maximum diffraction peak of perovskite structure
XRD of LaNi
0,3
Fe
0,7
O
3
(a) et LaNi
0,7
Fe
0,3
O
3
(b)
Deviation of the peaks with increasing Ni content
103
XRD of LaNi
x
Fe
1-x
O
3
family (0 x 1)
* LaFeO
3
(f. JCPDS 37-1493) et LaNiO
3
(f. JCPDS 33-0711)






XRD of LaNi
x
Fe
1-x
O
3
for 32,0 s 2u s 33,5 :
(a) LaFeO
3
, (b) LaNi
0,3
Fe
0,7
O
3
, (c) LaNi
0,4
Fe
0,6
O
3
, (d) LaNi
0,5
Fe
0,5
O
3

(e) LaNi
0,7
Fe
0,3
O
3
, (f) LaNi
0,8
Fe
0,2
O
3
, (g) LaNiO
3
.


Progressive deviation of the peaks with x
2u

0
1000
2000
3000
4000
5000
6000
32 32,2 32,4 32,6 32,8 33 33,2 33,4
I
n
t
e
n
s
i
t

x=1
x=0,8
x=0,7
x=0,5
x=0,4
x=0,3
x=0
I
n
t
e
n
s
i
t
y

104
a
j
a c i
i=1
j
=

1
a
i
2
= (h
i
2
+ k
i
2
+ l
i
2
) * d
i
2

The six most intensive diffration peaks indexed in a cubic system :
(100), (110), (111), (200), (211) et (220)
Average lattice parameter in cubic system
3,83
3,84
3,85
3,86
3,87
3,88
3,89
3,90
3,91
3,92
3,93
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
x
a

(
A

)
Evolution of the average lattice parameter a
c
versus Ni content
x
105
References

J.P. Sibilia, A guide to materials characterization and chemical analysis, Second
Edition, VCH Publishers Inc., 1996

B. Imelik and J.C. Vedrine, Catalyst characterization, Physical techniques for solid
materials, Plenum Press, New York, 1994

J.-P. Eberhart, Analyse structurale et chimique des matriaux, Ed Dunod, Bordas, Paris
1989

B. Imelik and J.C. Vedrine, Les techniques physisques dtude des catalyseurs, Ed
Technip, Paris 1988

X-Ray Methods, C. Whiston, 1987.

Modern Powder Diffraction, D.L. Bish and J.E. Post Eds., Reviews in Mineralogy Vol.
20,1989.

Methods and Pratices in X-Ray Powder Diffraction, JCPDS-International Centre for
Diffraction Data, 1989.

Introduction to X-ray Powder Diffraction Diffractometry, R. Jenkins and R.L. Snyder,
1996.

106
Part 3 : Spectroscopies
IR and UV spectroscopies applied to catalysis
107
Introduction to spectroscopy
The absorption of light is familiar to eveyone. The absorption of visible light is what makes
things coloured. For example a blue dye used in a pair of jeans appears blue because the light
at the red end of the spectrum is absorbed. This leaves the blue light to be reflected to the
observers eye.
108
I. Interaction of electromagnetic radiation (light) with molecules

1) Molecule energy is quantizied

Molecules have different states characterized by differences in energy

Ground state
Excited state
109

2) Light spectrum

Light has energy determined by its wavelength, , or frequency, v

c / = v and E = h v (c = 3 x 10
8
m/s, the speed of light; h = Planck's constant)
Thus, there is an inverse relationship between wavelength and Energy.
In the diagram below, gamma rays have the largest energy and radiowaves the smallest.

<-----Energy

110
If light striking a molecule in State 1 has an energy (h.v) equal to the difference in
energy between molecular State 1 (E
1
) and State 2 (E
2
), there is a probability that a
molecule will absorb a photon and jump to the higher energy state, State 2.


The molecule can jump back to state 1 by:
1) reemitting a photon of the same energy (or lower energy in the case
of fluorescence) or
2) transferring energy to another molecule

E
2
E
1
E
2
E
1
AE = E
2
E
1
= h.v
3) Light absorption by molecules
111
Light waves are described by sinusoidally oscillating electric vectors, E, and
perpendicular magnetic vectors, H. Hence, they are called Electromagnetic radiation

The probability of absorption is related to the orientations of E (and also H)
vectors with respect to the molecule. For now, assume that light waves and
molecules are randomly oriented.

4) Light : electromagnetic radiation
112
5) What magnitudes of energies are involved?

113
Outline
I. Introduction to IR-spectroscopy
1) Brief historical background
2) Principle of the techniques
3) Uses of Infrared spectroscopy
4) Nature of the samples

II. Theory about molecular vibrations
1) Introduction
2) First approach
3) Real diatomic molecule
4) The vibrations of polyatomic molecules

III. Interaction of light with a sample
1) Beer-Lamberts law
2) Nature of interactions

IV. Experimental part
1) The apparatus
2) Mathematical treatment : Fourier Transform
3) IR spectrum : Example of CO
2
4) Methods used for IR spectroscopy

V. Applications of IR spectroscopy
IR-spectroscopy
114
I. Introduction to IR-spectroscopy
1) Brief historical background

1905 Coblenz obtained the first IR spectrum
1940 Terenin and Kasparov made the first attempt to employ IR in adsorption
studies
1952 KBr was used for solid discs preparations for powder analysis
1960s the era of Fourier transfom IR (FT-IR) began


2) Principle of the technique

The principle of IR spectroscopy is similar to UV spectroscopy but the energy
scale is much lower (2-40 kJ/mol) and the wavenumber (200-4000 cm
-1
).
The energies correspond to transition energy between different vibrationnal
(and rotational) states of molecular bond.
J. Ryczkowski, Catalysis Today 68 (2001) 263-381
115
3) Uses of Infrared spectroscopy

IR spectroscopy can be used to :

Identify materials
Determine the composition of mixtures
Provide information helpful in deducing molecular structure
(functional groups)
Give information about superficial properties of solid catalysts
(surface hydroxyl groups, acidity)
Monitor the course and extent of reactions (in situ IR)
(reactional intermediates, changes in surface properties)
4) Nature of the samples

Materials in solid, liquid or gaseous state may be studied by IR
spectroscopy. A convenient sample size is several milligrams, but spectra
can be obtained from some picograms with special techniques.
116
Atoms in molecules and solids do not remain in fixed relative positions but vibrate about
some mean position. This vibrational motion is quantized and at room temperature, most
of the molecules are in their lowest vibrational state.
II. Theory about molecular vibrations
Absorption of electromagnetic radiation with the appropriate energy (infrared light) allows
the molecules to become excited to a higher vibrational level. The absorption of infrared
light as a function of wavelength give rise to an infrared spectrum with specific
fingerprints, assignable to particular molecular entities.
1) Introduction
hv
117
2) First approach : model of harmonic oscillator for diatomic molecule
a) classical mechanics
m
1
m
2
Schematic representation of a chemical bond considered as a
spring, wich exerts a force F on an atom
F = - k (r r
eq
)
The potential energy close to the equilibrium position is V(r)
The application of the fundamental dynamic principle leads to
With u the reduced mass of the molecule
2 1
2 1
*
m m
m m
+
= u
With k the force constant (N.m
-1
)
r : interatomic distance
r
eq
: interatomic distance at equilibrium
r
118
The resulting vibrational energy is
) (
2
1
eq vib
r r k E =
And the wavenumber
=
=
c
v
The wavenumber depends on two parameters :

Reduced mass m
Wavenumber decreases with heavier atoms

Ex :


Force constant k
Wavenumber increases with stronger bonds

Ex:
119
b) Quantum mechanics applied to diatomic molecule
The harmonic vibration of a diatomic molecule is treated by solving the Schrdinger
equation :
The solution of this equation is that vibrational energy is quantized according to :
u t
v
k
2
1
=
and n an integer number
n = 0, 1, 2
called vibrational quantum number
At any temperature T, the molecular vibrations are distributed over the energy levels
according to Boltzmanns law :

|
.
|

\
|
+
=
kT
h n
N N
T n
v
2
1
exp .
N
n
is the population of vibrational level n
)
2
1
( + = n h E
n
v
120
3) Real diatomic molecule : anharmonic oscillator
The deviations of the real potential energy curve from that of the harmonic oscillator is
called anharmonicity and is due :

- to electronic repulsion for r < r
eq
- to electronic rearrangements as the atoms move further and further apart for r > r
eq


The treatment of anharmonic ocillators leads to the quantum mechanical expression of
energy :

v v h x n n h E
a n
)
2
1
( )
2
1
( + + =
X
a
is called anharmonicity constant
harmonic
oscillator
anharmonic
oscillator
121
How is it possible to extract information about the composition of a compound
Using IR spectroscopy?

When a IR radiation is sended to a sample, each molecule will absorb part of the
radiations having convenient wavelength so that it can be excited to a higher
vibrational and rotational state.

To each functional group of a molecule correspond defined vibrations and rotations,
which depend on the geometry of the molecule, number of atoms, nature of atoms,
environment
and which are characteristic of the functional group.
The energies involved for these vibrations can be known by calculation or
experiments.

If we can determine the energy absorbed by the sample in a wide enough range of
IR wavelengths, we should be able to identify the functional group responsible for
each defined absorption and determine the composition of the sample.


This is the aim of IR spectroscopy


122
4) The vibrations of polyatomic molecules
Which are the characteristic vibrations of molecules?

a) number of normal vibration modes

When N independently moving atoms are combined in a molecule, in 3D space
the 3N degrees of freedom are transformed into :

- 3 degrees of translational freedom
- 3 degrees for rotation (or only two for linear molecules)
- the rest for vibrations

Molecule
with N atoms
Linear : 3N 5 vibration modes
Non-linear : 3N 6 vibration modes
123
b) name of the vibration modes
stretching
1) Bond deformation
2) Angle deformation
* in the plane
symmetrical
stretching
antisymmetrical
stretching
* out of the plane
wagging
twisting
3) Ring deformation
breathing
bending
or scissors
v
v
s
v
as
o

|

p

rocking
Except for rings,
molecules N 1 bonds
with N 1 stretching
N atoms 2N 5 (or 4) angle
vibrations
124
Example 1 : H
2
O vibration modes
Non-linear molecule with 3 atoms 3*3-6=3 normal vibration modes
(3657 cm
-1
)
(1595 cm
-1
)
(3756 cm
-1
)
2 stretching
and 1 bending
vibrations
125
Example 2 : CO
2
vibration modes
Linear molecule with 3 atoms 3*3-5=4 normal vibration modes
2 stretching
and 2 bending
vibrations
126
d) Criteria for bond assignement in IR spectroscopy
1) Table of group frequencies
2) Strength of the bonds
3) Stretching versus bending vibrations
4) Mass of the atoms
c) Rules in IR spectroscopy
1) The force constant of a stretching vibration is larger than that of a
bending vibration
frequency of stretching > frequency of bending for a group
2) Frequency increases if the mass of the atoms decreases
3) Frequency increases if the bond strength increases
4) Normal vibrations may have the same frequency
they are degenerate
5) Some vibrations are forbidden according to Laportes selection rule :
vibrations which induce a change in dipole moment are allowed in IR
(homonuclear diatomic molecules like O
2
, N
2
are inactive in IR)
127
128
Examples :
129
Possible identification of functional groups using IR

Applications of IR spectroscopy :

Identify materials
Determine the composition of mixtures
Provide information helpful in deducing molecular structure
(functional groups)
Give information about superficial properties of solid catalysts
(surface hydroxyl groups, acidity)
Monitor the course and extent of reactions (in situ IR)
(reactional intermediates, changes in surface properties)
How can it be made practically?
130
III. Interaction of light with a sample
Sample
Detector
The relation between I and I
0

is given by the Beer-Lambert Law
Defining A

absorbance
log (I
0
/I) = A

= c

c l
When light with an incident intensity I
0
is directed to a sample, a part is absorbed
by the sample I
0
-I and the intensity of the transmitted light I is a function of the
sample thickness l, of the concentration c of absorbing molecules in the sample and
of the exctinction coefficient c

.
1) Beer-Lamberts law (case of diluted liquid)
Measurements of I and I
O
permit to
access to the absorbed part
131
It is possible to extract absorbing properties of the sample from
the transmitted light
However reflection and scattering should not always be neglicted
2) Nature of interactions between light and sample
132
fraction of reflected light can be eliminated using a reference
measurement with same materials (cuvette + solvent or diluting species)
a) How to limit reflection?
Reference
Sample
133
scattering is negligible in molecular disperse media (solutions)

scattering is considerable for colloids and solids when the
wavelength is in the order of magnitude of the particle size
scattering is reduced through embedding of the particles in media with
similar refractive index: KBr wafer
b) What about scattering ?
Scattering is important for solids (3-40 mm) : Can we use it ?
134
Material transparent in some areas of IR wavelengths
135
IV. Experimental part
1) The apparatus
2 types of spectrometers :

a) Dispersive IR instrument
For many decades, the workhorse of the IR laboratory was the light dispersive spectrometer.
While still used for routine experiments, it has been superseded by the Fourier Transform
Infrared (FT-IR) spectrometer, which employs an interferometer in place of a monochromator.
IR source
(SiC)
136
http://spectroscopy.lbl.gov/FTIR-Martin/FTIR-Martin_files/frame.htm
b) FT-IR spectrometer with Michelson interferometer
137
2) Mathematical treatment : Fourier Transform
In continuous scan mode the moving mirror is repetitively scanned as fast as 1/20e second
to generate the Fourier transform of the IR spectrum. After coaddition of many scans (meanly 32)
To improve the signal-to-noise ratio, the Fourier transform is converted to the IR spectrum by a
dedicated computer.

+

= dx x x G g ) 2 cos( ) ( ) ( tu u
The Fourier transfom of G(x) is
138
3) IR spectrum : Example of CO
2
v
as
CO
2349cm
-1
v
s
CO
1537cm
-1
o CO
667cm
-1
v
as
CO
2349cm
-1
v
s
CO
1537cm
-1
o CO
667cm
-1
absent
139
4) Methods used for IR spectroscopy
a) Transmission spectroscopy
Transmitted light is analyzed
140
Uses of transmission spectroscopy
This technique can be used for gas, liquid or transparent solid samples

For liquids, 1cm long cells with 2 transparent
faces are used (CaF
2
)
For gases, several centimeter long cells
with 2 windows are used.


In the particular case of solid catalysts, the sample is mostly as a powder and has to be
sieved and pressed together to form a thin pellet (diameter about 18mm, thickness 10
-2
5.10
-2
mm)

The pellet can be placed on a quartz support in a special cell, which allows to keep the sample under
controlled atmosphere and controlled temperature
Part A is equipped with IR transparent windows, where the pellet is maintained during spectrum record
Part B (in quartz or pyrex) is used for thermic treatment
141
Problem : not transparent enough samples can not be analysed
using transmission !
Possible dilution :
it can be diluted in a transparent
and inert compound like KBr, SiO
2



Other techniques : use of reflection
Incident light should not be perpendicular to the sample surface
I and Io not in the same direction
142
b) Reflection spectroscopy
Instead of measuring the transmitted light, it is possible to measure the
reflected light. This is more convenient for dark samples.

Can we extract the absorption properties of our sample from the
reflected light?
143
particle diameter d >

light partially reflected on elementary mirrors (crystal facets) inclined
statistically at all possible angles to the macroscopic surface

light penetrates into sample, undergoes numerous reflections, refractions
and diffraction and emerges finally diffusely at the surface
particle diameter d

scattering occurs
multiple scattering should produce isotropic distribution
1) Particle size effect :
Possible analysis by specular reflection
Possible analysis by diffuse reflection
144
2) Diffuse Reflectance (DRIFT)
Diffuse reflectance is the radiation, which penetrates into the sample and then emerges.
This technique needs :
element that collects diffusely reflected light
to avoid specularly reflected light
reference standard (white standard)
Used for
Low reflecting samples
Powder particle diameter <
145
Cooling water (in) Cooling water (out)
Pictures of DRIFT cell
Scheme of
DRIFT cell
Well adapted to in situ characterisation in heterogeneous catalysis
146
Diffuse Reflectance (DRIFT)
This system is designed so that diffuse reflectance is optimized and specular minimized.
147
3) Specular reflection
This is a mirror-type reflection
fraction of reflected
light increases with o
| depends on o and
ratio of the refractive
indices (Snell law)
This technique is used for the study of thin metallic films, monocrystals,
Surfaces with low rugosity (<<)
n
0
sino = n
1
sin|
148
4) Attenuated Total Reflectance (ATR)
This method permits to study non transparent samples (fine powder or liquids).
The sample is held in optical contact with a prism (transparent monocrystal with high refraction
index (N>24) like Ge, ZnSe, CaF
2
) and the light entering the prism undergoes internal reflection at
the prism surfaces and penetrates into the film. So the exiting light is attenuated at specific
frequencies corresponding to absorption by the film sample.
5) Photoacoustic Spectroscopy (PAS)
In PAS the IR energy absorbed by the sample is converted into heat. Thermal conduction to the sample
Surface induces expansion of gas in contact with it and produces an acoustic signal (proportional to the
absorption) when the incident beam intensity is modulated at a frequancy in the acoustic range.

Applications include analysis of surface coatings, alumina-based catalysts, as well as obtaining the
IR spectrum of opaque materials.
149
6) Recent development :
optic fibers
This system allows to follow a
reaction in liquid phase in situ
light conducted through total reflectance
150
Large number of applications of IR spectroscopy in catalysis and surface science
V. Applications of IR spectroscopy
(coupling)
151
IR spectra of CH
4
adsorbed
on modified MgO samples
at 0.08 kPa and 88K
Example 1 : CH
4
adsorption on modified MgO samples


Deviation of wavenumber
in comparison to gas phase due to
interaction with modified MgO :
the interaction between
methane and the Cs-containing
MgO catalyst is the strongest.
J. Ryczkowski / Catalysis Today 68 (2001) 263381 281
v
as
CH
3
(gas 3020 cm
-1
)
Effect of doping
materials :
v
s
CH
3
(gas 2914 cm
-1
)
152
FT-IR spectra of pyridine adsorbed on zeolites (A) USY (a) and MCM-41 (b)
And (B) amorphous silica-alumina (a) and MCM (b) degassed at (1) 200C, (2) 300C and (3) 400C
(A) : USY has a higher amount of Brnsted acid sites than MCM-41 zeolite
(B) : MCM-41 has a higher amount of Lewis sites than amorphous Si-Al
A B
Example 2 : evaluation of the acidity of Si-Al catalysts
Ref : A. Corma et al., J. Catal., 1994, 148, 569
153
Influence of the covering rate on vCO vibration frequency
Influence of the composition of the
12
CO-
13
CO on vCO frequency
vCO deviates from 2063 to 2100 cm
-1

when the CO covering rate over Pt [111]
increases.
1)Metal CO bond strength decreases
and CO bond strength increases
2)CO-CO dipolar interactions increases
vCO deviates from 2063 to 2100 cm
-1

when the
12
CO content increases and
the
13
CO content decreases
Due to CO-CO dipolar interactions
Ref : Crossley A.,King D.A., Surf.Sci., 68, 1977, 528
2 possible explanations :
Isotopic exchange should only influence CO-CO dipolar
Interactions and not Me-CO bond strength
Here :
Example 3 : Isotopic dilution
154
Example 4 :
Transition between physisorbed
and chemisorbed CO on ZrO
2

with increasing T
IR band at 2185 cm
-1
observed at Ta =
300K corresponds to linear CO. At 300 K
a purge leads to the disappearance of the
IR band indicating that CO is reversibly
adsorbed.
The increase in T (spectra bh) under CO,
leads to a progressive decrease
in intensity of the IR band alongside a
slight shift to higher wavenumbers (2187
cm
-1
at 340K and 2190 cm
-1
at 378 K)
due to chemisorption.
J. Ryczkowski / Catalysis Today 68 (2001) 263381 281
155
Example of in situ IR measurements
J. Ryczkowski / Catalysis Today 68 (2001) 263381 281
156
Study of metallic alloy M
1
-M
2
Geometric effect :
Electronic effect :
M
2
addition leads only to an
increase in the distances between
CO-M
1
vibrations
M
2
addition modifies only the
electronic density of M
1

Ref : Toolenaar et al., J. Catal., 82, 1983, 1
Some alloys show different catalytic properties than pure metals. It can be due to :
x =
12
CO/(
12
CO +
13
CO)
Shape of the curve vCO versus x gives the information
Test : CO adsorption on M
1
and alloy with isotopic dilution
157
Comparison : Transmission - Diffuse Reflectance
spectra can have completely different appearance
transmission decreases, reflectance increases with increasing wavenumber
158
vibrations of surface species may be more evident in DRIFT spectra
Comparison : Transmission - Diffuse Reflectance
absolute reflectance R
absorption coefficient k
scattering coefficient s
Kubelka-Munk Function
159
In conclusion : What can we learn from IR?
160
W. WM. Wendlandt, H.G. Hecht, Reflectance Spectroscopy,
Interscience Publishers/John Wiley 1966


B.M. Weckhuysen, P. van der Voort, G. Catana, Spectroscopy of transition metal ions on
surfaces, Leuven University Press 2000


J.P. Sibilia, A guide to materials characterization and chemical analysis, Second Edition,
VCH Publishers Inc., 1996
References
P. W. Atkins, Physical Chemistry, Oxford University Press


The science of spectroscopy : http ://www.scienceofspectroscopy.info.


Spectroscopy Now : http ://www.spectroscopynow.com.
161
Outline
I. Introduction to UV-spectroscopy
1) General
2) Shape of the peaks
3) Why using UV-spectroscopy ?
4) Form of the samples :

II. Measurements
1) Instrumentation
2) Techniques
3) Quantitatively

III. What Electronic properties lead to absorption of UV-Light?
1) Example
2) Nature of the electronic transitions

IV. Examples of UV spectroscopy applications in catalysis
UV-spectroscopy
162
1) General

1. UV (ultraviolet) radiation: = 190 - 400 nm Visible: = 400 - 800 nm



2. This corresponds to approximately 400 kJ/mole of photons, the magnitude of
energy in a covalent bond.

3. Energies of these magnitudes correspond to electronic transitions
==> promotion of an electron from one molecular orbital to an unoccupied
molecular orbital of higher energy.

Absorption of a photon of light has a high probability of occuring when the
orientation of the electric vector of the light wave, E, is oriented in a direction which
will induce a movement of an electron from one molecular orbital to another oribital
of higher energy.

Another way of stating this is to say that E is oriented along a Transition Dipole of
the molecule.

E = h.v = h.c / = 6.626.10
-34
*3.10
8
/ 300.10
-9
= 6.626 .10
-19
J / photon
I. Introduction to UV-spectroscopy
163
For a single type of transition between two well-defined states, the Absorbance
spectrum would be a very sharp peak.

In practice, there are a range of possible transitions from various vibrational energy levels
of the ground state to various vibrational energy levels in the first excited state

==> a series of narrow absorption peaks of similar energies ; these cannot be resolved
resulting in a single broad and sometimes complex peak for each type of electonic
transition.

2) Shape of the peaks
164
3) Why using UV-spectroscopy ?
Ultraviolet/visisble spectroscopy is a useful analytical
technique.
It can be used :
- to identify some functionnal groups in molecules
- to assay (determine the content and strength of a substance :
trace metal content in alloys)
- to provide information about the electronic structure
(especially for aromatic and transition metal compound)
165
4) Form of the samples :

Liquids and solids are analyed as neat materials or in dilute
solutions, where a wide variety of solvents can be used

Vapors are examined directly

The sample for UV spectroscopy are prepared like those for IR
spectroscopy

The sample size required is typically of the order of 1mg, but in
special applications in the UV region, spectral information can be
obtained from nanogram amounts
166
II. Measurements

1) Instrumentation

a) Single Beam Spectrophotometer



167

b) Split Beam Spectrophotometer



This system should have 2 detectors. It is possible to use only 1 detector and
read I and Io successively

168
Two lamps are used :
- a hydrogen or deuterium lamp for the ultraviolet region
- a tungsten/halogen lamp for the visible region
169
A reference cell containing only reference material (gas, solvent) is used.

For double beam instruments, light is passed simultaneously through the
sample cell and the reference cell. The spectrometer compares the intensities of
light passing through the sample and of light passing through the reference cell.

The transmitted or reflected radiation is detected and the spectrometer records
the absorption spectrum by scanning the wavelength of light passing through
the cells.

For single beam instruments, the principles are the same, but data on the
reference are taken first, followed by the sample.
170
Fotograph of a UV-Vis spectrometer
171
It is possible to make measurements by :

1) Transmission :
This technics is available for liquids, gases or transparent solids
Light is passing through the sample and the transmitted light is analysed.

Absorbance id defined as : A = log (Io / I)
with I = intensity of transmitted beam
And Io = intensity of incident beam

2) Reflection
This method is used for solid samples (catalysts), surfaces (painting) or trouble
suspensions, which are not transparent enough to be analysed by transmission.
Two kinds of reflection exist :
- specular reflection (mirror effect of the crystals)
- diffusive reflection (diffusion of the light in all space)

Reflectance is defined : R = I / Io
2) Techniques
172
3) Quantitatively

For light passing through a solution, the rate at which photons are absorbed as a function
of distance, l, through the sample cuvette can be thought of as a 1st order reaction and is
proportional to the concentration, c, of absorbing molecules with a rate constant called c'.
Thus:

This is the Beer-Lambert Law
change to log10
A

= c

c l where A and c are for a specific wavelength,

173
III. What Electronic properties lead to absorption of UV-Light?

1) Example : a simple molecule : Formaldehyde => H
2
C=O

a) Electronic Configuration:

C -- 1s
2
2s
2
2p
y
1
2p
x
1
2p
z
0
----->1s
2
(3sp
2
)
3
2p
z
1

O -- 1s
2
2s
2
2p
y
2
2p
x
1
2p
z
1


C uses 3 sp
2
hybrid orbitals to form 3 o-bonds with O and the 2 H's ; the
remaining 2p
z
orbital forms a t bond with O. O has the 2p
y
atomic orbital
which is not involved in bonding, and it contains a non-bonding pair of
electrons.



174

b) Molecular Orbital Diagram
only higher energy orbitals are shown




n = non-bonding orbital (O 2p
y
)
t = bonding orbital (C 2p
z
+ O 2p
z
)
t* = anti-bonding orbital (C 2p
z
- O 2p
z
)

c) Quantum Mechanics:

t ---> t* transition is "allowed" and will occur when E is parallel to the x axis
n ---> t* transition is "symmetry forbidden" ==> transition does not induce a dipole
change in the molecule. This transition does occur because of limitations in theory
used to predict transitions but with very low probability, <1% of t ---> t*.

175
2) Nature of the electronic transitions
The electronic transitions are found in organic or inorganic chemistry and
can be classified in different groups
1) d-d transitions :
They are found in transition metal ions, when they are complexed
by coordinates (Energy of the d orbitals depends on the nature,
structure of the complex) and when d level is not full

2) charge transferts
Transitions between molecular orbitals centered on different
atoms : electron transfer between metal and ligand

3) Transitions t t* and n t*
Electronic transfer between molecular orbitals in organic
molecules
176
IV. Examples of UV spectroscopy applications in catalysis
Catalyst Deactivation: in situ UV-vis Spectroscopy
formation of additional bands during n-butane isomerization
band at 310 nm, allylic cations? Analyzed using apparent absorption A=1-R
spectroscopic and catalytic data can be correlated
177
W. WM. Wendlandt, H.G. Hecht, Reflectance Spectroscopy,
Interscience Publishers/John Wiley 1966


B.M. Weckhuysen, P. van der Voort, G. Catana, Spectroscopy of transition metal ions on
surfaces, Leuven University Press 2000


J.P. Sibilia, A guide to materials characterization and chemical analysis, Second Edition,
VCH Publishers Inc., 1996
References
P. W. Atkins, Physical Chemistry, Oxford University Press


The science of spectroscopy : http ://www.scienceofspectroscopy.info.


Spectroscopy Now : http ://www.spectroscopynow.com.