05

Electron
Microscopy
 Electron Microscopy
Electron Microscopy
• Electron microscopy is a rather straight
forward technique to determine the size
and shape of supported particles.
• Electrons have characteristic wavelengths
of less than 1 A˚, and come close to
monitoring atomic detail.
• Thus, the interaction of the primary beam
with the sample provides a wealth of
information on morphology,
crystallography and chemical
composition. Using transmission electron
microscopy to make a projection of the
sample density is a routine way to study
particle sizes in catalysts.
Electron
microscopy

Figure 7. Interaction
between the primary
electron beam and the
sample in an electron
microscope leads to a
number of detectable
signals.
Electron Microscopy

Types of Electron Microscopy

1- Transmission Electron
Microscopy (TEM).

2- Scanning Electron
Microscopy (SEM).
 Schematic set up of an electron microscope in the transmission

Electron (TEM) and the scanning (SEM) mode. The SEM instrument also
contains an X-ray detector for composition analysis.
Microscopy
 06
Mossbauer Spectroscopy
 Mossbauer spectroscopy provides the oxidation
Mossbauer state,
Spectroscopy the internal magnetic field, and the lattice
symmetry of a limited number of elements such
as iron, cobalt, tin, iridium, ruthenium, antimony,
platinum and gold,
The Mssbauer effect, discovered by Rudolf L. Mssbauer in 1957, can in short be
andascan
described the be applied
recoil-free in situ.
emission and resonant absorption of gamma radiation
by nuclei.

 Formation of Gama rays

Instrumentation

Doppler Effect
Mossbauer
Spectroscopy
Application

EX: catalyst Fe/ TiO2 for fischer-Trpsch synthesis

1- Fresh catalyst after impregnation and drying
2- reduction of catalyst
3- catalyst after synthesis
4- catalyst exposed to air
Mossbauer
Spectroscopy Importance

Quantitative determination of valence state of

iron in material
Identification of various iron oxide
Determination of coordination number of Fe
atoms
Determination element such as Sn and Sb
Mossbauer
Spectroscopy Limitation

Sample must be solid state

Don’t detect or identify all elements
 07
Temperature-programmed
Reduction, Oxidation and
Sulfidation
 • Temperature-programmed reaction methods form a
Temperature- class of techniques in which a chemical reaction is
programmed monitored while the temperature increases linearly
in time.
• Several forms are in use: temperature-programmed
reduction, oxidation and sulfidation.
• The instrumentation for temperature-programmed
investigations is relatively simple. The reactor,
charged with catalyst, is controlled by a processor,
which heats the reactor at a linear rate of typically
0.1 to 20 C min–1. A thermal conductivity detector
or, preferably, a mass spectrometer measures the
composition of the outlet gas.
• TPR provide useful information on temp needed for
complete reduction of catalyst
• EX: silica supported iron and rhodium catalyst
Temperature-
programmed
Notes

1- difference in reduction temp between rhodium

and iron
2- area under TPR curve represent total hydrogen
consumption
3- TPR of bimetallic catalyst is reduced at low
temp than iron catalyst
Rhodium dissociate hydrogen
Atomic hydrogen migrates to iron oxide and
reduce oxide
Temperature- Temperature-programmed
programmed
Sulfidation

• Catalyst used for

hydrodesulfurization(HDS) and
hydrodenitogenation(HDN) of heavy oil
fraction
• Alumina-supported molybdenum or
tungsten
• Cobalt or nickel is added as a promotor
• Catalyst are active in sulfided state
Temperature-
programmed

• Treating oxides catalyst in mixture of H2S + H2

• Hydrogen prenvent decomposition H2S to
elemental sulfer
• Process under 500 kelvin
• Process at 500 kelvin
 08
IR spectroscopy
 • Used to detect functional groups in compounds
IR spectroscopy • Used in catalyst to identify adsorbed species and to
study way these species are chemisorbed on surface
on catalyst
• Transitions between vibrational levels occur by
absorption of photons with frequencies in the infrared
range (wavelength 1–1000 mm, wavenumbers 10,000–
10 cm–1, energy differences 1240–1.24 meV).
• Infrared portion
1- near infrared (1400-4000 cm-1)
2- mid infrared(4000-400 cm-1)
3-far infrared (400-10 cm-1)
IR spectroscopy
Factors affecting on frequency

1- conjugation

2- donating and withdrawing group

3- size of ring
IR spectroscopy Types of IR vibration

1- stretching vibration (change bond length)

Need relativity high energy
Have symetrical and asymetrical types

2- bending vibration (change bond angle)

Need low energy
Scissoring , rocking , wagging and twisting
IR spectroscopy Application on carbonyl
CO molecule + heavy substitution
=increase frequencny by 20-50 cm-1
CO molecule + its image in
conducting polarizable = decrease
frequency by 25-75 cm-1
CO molecule + substrate form
chemisorption bond = weakness
frequency
 09
Surface
Science
Techniques
Low Energy
Electron Diffraction
(LEED)
- Low Energy Electron
Diffraction (LEED)

• Low Energy Electron Diffraction (LEED)-

LEED is the surface analogue of X-ray
diffraction , it's a technique for the
determination the arrangement of atom
close to surface .
• Depends on the dual nature of the
electron- use electron with energy 20 -200
ev
- Low Energy
Electron
Diffraction
(LEED)
- Low Energy
Electron
Diffraction
(LEED)
- Low Energy
Electron
Diffraction
(LEED)
 Scanning probe microscope

- It's one of the most important technique in studying

the surfaces and used at nanoscale level.
- It don't have a direct view of the surface but an
image representing the surface structure is created
in 3D.
- It is the examination of the surface of a material
using a probe with an atomic sharp tip.
- There is two types of SPM:
1- Scanning tunneling microscopy (STM).
2- Atomic force microscopy (AFM)
These techniques are capable of imaging
the local surface topography with atomic
resolution
 Scanning tunneling microscopy (STM)

- It used a very sharp tip with an atomic end up to one

atom is brought close to a surface.
- The distance between sample and tip below 0.5nm.
- The electric tunneling current will flow when applied a
small voltage , This current depends on the distance
between surface and tip.
- By changing in current in current it create an image
about surface
 Scanning tunneling microscopy (STM)

By acquiring
subsequent
pictures it is
possible to
make movies of
dynamical
processes on
the surface,
such as
diffusion or
chemical
reaction.
• Unfortunately, STM only
works on well defined, planar,
and conducting surfaces such
as metals and
semiconductors, and not on
oxide-supported catalysts.
• For the latter surfaces,
atomic force microscopy
offers better perspectives.
 2- Atomic force microscopy (AFM):

- It is a modification of (STM) in 1986 , It depends

on attractive and repulsive force between atom.
- it use a small nano size tip to can be effected by
thia force.
- This oscillation of cantilever detected by laser and
detection to give a 3D image about surface.
2- Atomic force microscopy (AFM):
In this chapter we have limited ourselves to the most
common techniques in catalyst
characterization. Of course, there are several other
methods available, such as
nuclear magnetic resonance (NMR), which is very
useful in the study of zeolites,
electron spin resonance (ESR) and Raman
spectroscopy, which may be of interest
for certain oxide catalysts. Also, all of the more generic
tools from analytical chemistry,
such as elemental analysis, UV–vis spectroscopy,
atomic absorption, calorimetry,
thermogravimetry, etc. are often used on a routine
basis.