CATALYSIS

Catalyst Characterization
 Introduction:
• Characterization is an important field in
catalysis.
• Spectroscopy, microscopy, diffraction
and methods based on adsorption and
desorption or bulk reactions (reduction,
oxidation) all offer tools to investigate
the nature of an active catalyst.
• With such knowledge we hope to
understand catalysts better, so that we
can improve them or even design new
catalysts.
Catalyst
Characterization

Catalyst Characterization
importance:

the ultimate goal of catalyst

characterization should be to:
examine the surface atom by atom
under the reaction conditions
under which the catalyst operates.
Catalyst
Characterization

Catalyst Characterization:
• catalyst often consists of small
particles of metal, oxide, or sulfide
on a support material.
• Chemical promoters may have
been added to the catalyst to
Optimize its activity and\or
selectivity.
• structural promoters may have
been incorporated to improve the
mechanical properties and
stabilize the particles against
 Figure 1. Supported catalyst, consisting of small particles on
Catalyst a high surface area carrier such as silica or alumina, along with
two simplified model systems, which in general offer much
Characterization better opportunities for characterization at the molecular level.
 Figure 2. Catalyst characterization techniques: The circle represents the
Catalyst sample under study, the inward arrows denote excitation processes,
and the outward arrows indicate how the information should be extracted.
Characterization
 02
X-RAY DIFFRACTION
(XRD)
X-RAY
DIFFRACTION
(XRD)
X-RAY DIFFRACTION
(XRD)

• It is used to identify crystalline phases

inside catalysts.
• X-ray diffraction occurs in the elastic
scattering of X-ray photons by atoms in
a periodic lattice .
• The scattered monochromatic X-rays
that are in phase give constructive
interference.
X-RAY
DIFFRACTION Bragg’s Equation
(XRD)
nʎ=2dsinθ

Where:
• ʎ is the wavelength of the X-rays.
• d is the distance between two lattice
planes.
• θ is the angle between the incoming
X-rays and the normal to the
reflecting lattice plane.
• n is an integer called the order of
the reflection.
• Diffractograms are measured as a
Figure 3.
function of the angle 2θ.
X-RAY
DIFFRACTION
(XRD) XRD IN Catalyst
Characterization
• In catalyst characterization,
diffraction patterns are mainly used to
identify the
crystallographic phases that are
present in the catalyst.
• Fig 4. gives an example where XRD
readily reveals the Pd reflections in
two Pd/SiO2 catalysts.
X-RAY XRD IN Catalyst Characterization
DIFFRACTION
(XRD)

Figure 4.
X-RAY
DIFFRACTION
(XRD) XRD IN Catalyst
Characterization
• XRD can be used to study catalysts
under realistic conditions in specially
designed
in situ reactors.
• This enables one to monitor solid-
state reactions such as reduction,
oxidation and sulfidation that play a
role in the activation of catalysts.
X-RAY
DIFFRACTION
(XRD)
Strength of XRD in
Catalyst Characterization

The strength of XRD for catalyst

characterization is that:
• it gives clear and unequivocal
structure information on particles that
are sufficiently large, along with an
estimate of their size, and it can
reveal this information under reaction
conditions.
X-RAY
DIFFRACTION
(XRD)
Limitation of XRD
The limitation of XRD is that:
• It can not detect particles that are either too
small or amorphous.
• Hence, one can never be sure that there are
no other phases present than the ones
detected with XRD. In particular, the surface,
where catalytic activity resides, is invisible in
standard XRD.
 03
X-RAY PHOTOELCTRON
SPECTROSCOPY (XPS)
X-RAY
PHOTOELCTRON
SPECTROSCOPY
(XPS)
X-RAY PHOTOELCTRON
SPECTROSCOPY (XPS)

• XPS is among the most frequently used

techniques in catalysis.
• It yields information on the elemental
composition, the oxidation state of the
elements and, in favorable cases, on the
dispersion of one phase over another.
X-RAY
PHOTOELCTRON
SPECTROSCOPY
(XPS) X-RAY PHOTOELCTRON
SPECTROSCOPY (XPS)
• XPS is based on the photoelectric effect:
An atom absorbs a photon of energy hʋ so
that a core or valence electron with binding
energy 𝑬𝒃 is ejected with kinetic energy(Fig.
5.):
where: 𝑬𝒌 = hʋ − 𝑬𝒃 − 𝝋
- 𝑬𝒌 : the kinetic energy of the photoelectron.
- h: blank constant.
- ʋ: frequency of the exciting radiation.
- 𝑬𝒃 : the binding energy of the photoelectron
- 𝝋: work function of the spectrometer
X-RAY
PHOTOELCTRON Fig. 5. X-RAY PHOTOELCTRON SPECTROSCOPY (XPS)
SPECTROSCOPY
(XPS)
• In XPS one measures the intensity of photoelectrons N(E)
as a function of their kinetic energy.
X-RAY
PHOTOELCTRON
SPECTROSCOPY
(XPS)
X-RAY PHOTOELCTRON
SPECTROSCOPY (XPS)
• Binding energies are not only element
specific but contain chemical information
as well, because the energy levels of
core electrons depend slightly on the
chemical state of the atom.
Because XPS is a surface sensitive
technique, it recognizes how well
particles are dispersed over a support.
• Fig. 6. shows two catalysts with the same
quantity of supported particles but with
different dispersions.
 Figure 6. The XPS intensity ratio of signals from particles and
Catalyst the support, IP/IS, reflects the dispersion of the particles over
the support.
Characterization
Advantages of
X-RAY • XPS is among the most frequently used techniques in
characterizing catalysts.
PHOTOELCTRON
• It readily provides information about:
SPECTROSCOPY - the composition of the surface region.
(XPS) - both the oxidation state of metals and the
electronegativity of any ligands.
• XPS can also provide insight into the dispersion of
particles over supports, which is particularly useful if
the more common techniques employed for this purpose,
such as electron microscopy or hydrogen chemisorption,
can not discriminate between support and active phase.
 04
Extended X-Ray Absorption
Fine Structure (EXAFS)
Extended X-Ray
Absorption Fine
Structure (EXAFS)
Extended X-Ray Absorption
Fine Structure (EXAFS)

• EXAFS, like XPS, is based on the

absorption of X-rays and the creation of
photoelectrons.
• In XPS the photoelectrons are collected to
analyze their kinetic energy, whereas
EXAFS deals with the ways these electrons
are scattered by neighboring atoms, which
is visible in interference effects in the X-ray
absorption spectrum.
Extended X-Ray
Absorption Fine
Structure (EXAFS)
Extended X-Ray Absorption
Fine Structure (EXAFS)

• The technique yields detailed information

on the distance, number and type of
neighbors of the absorbing atom, and
thus gives insight into local structure
on the sub nanometer length scale.
• as X-rays have high penetrating power,
EXAFS offers attractive in situ
opportunities.
Rh/Al2O3 catalyst under hydrogen, after reduction at 200 and 400 C. The Fourier transforms
show the presence of Rh neighbors at 0.27 nm and oxygen neighbors at shorter distances.
The data analysis indicates that the catalyst reduced at 200 C still contains Rh–O
contributions characteristic of Rh2O3, which are attributed to unreduced particles. However,
the Rh–O contribution in the radial distribution function of the fully reduced catalyst is due to
contact between rhodium atoms and the oxygen atoms of the alumina support. In this way,
EXAFS can give information on the nature of metal support interactions.
Extended X-Ray
Absorption Fine
Structure (EXAFS)
Extended X-Ray Absorption
Fine Structure (EXAFS)

• An important requirement for meaningful

EXAFS data on catalysts is that the
particles are monodisperse, such that
the average environment, which
determines
the EXAFS signal, is the same
throughout the entire catalyst.
Extended X-Ray
Absorption Fine
Structure (EXAFS)

Limitation of (EXAFS)
• For multi-component catalysts, the
technique has the drawback that data
analysis becomes progressively more
complicated and time consuming with an
increasing number of constituent atoms,
and that considerable expertise is required
to avoid ambiguities.
• However, EXAFS of optimized and
monodisperse catalysts, for which the data
analysis is carried out with care, provides
unique structure information on the scale of