Catalyst Characterization

Catalyst Characterization
• Characterization figures out catalysts properties:

physical, chemical and catalytic performance
• Characteristics include:
• (1) chemical composition
• (2) area
• (3) porosity
• (4) particle size
• (5) crystallinity
• (6) morphology
Catalyst Characterizations: Structural
• Surface area : Brunner – Emmet – Teller (BET)

method
• Pore analysis: mercury intrusion method
• Crystallinity: X-Ray Diffraction (XRD)
Catalyst Characterizations: Thermal
• Thermal property (melting point, latent heat) :

Differential Scanning Calorimetry (DSC)
• Weight loss or gain due to temperature change:
Thermal Gravimetry Analysis (TGA)
• Reduction of metal: Temperature Programmed
Reduction (TPR)
Catalyst Characterizations: Spectroscopy
• Molecular structure and bonds: Infra – Red

(FTIR/ATR)
• Oxidation state and metal interactions :
Raman Spectroscopy
Catalyst Characterizations: Morphology, Topography
(Form and Structure)
• Scanning Electron Microscopy (SEM):

resolution > 5 nm
• Transmission Electron Microscopy (TEM):
resolution > 0.2 nm
BET Analysis
• Based on theory of Stephen Brunauer, Paul
Emmett, Edward Teller (J of ACS 60, 1938)
• Theory aims to explain adsorption of gas
molecules on solid surface
• BET theory holds hypothesis of:
• (a) infinite layer of gas on solid surface
• (b) independent interaction between layers
• (c) Langmuir behavior in each layer
BET Analysis
• BET method commonly uses adsorption of nitrogen
on the solid surface/pore
• Range :
Catalysis & Catalysts
Adsorption On Solid Surface

• Use of BET isotherm to determine the surface area of a solid
– At low relative pressure P/P0 = 0.05~0.35 it is found that
P / P0
P / P0 1 c 1 V (1 P / P0 )
  ( P / P0 )
V (1  P / P0 ) cVm cVm
P/P0
Y = a + b X
• The principle of surface area determination by BET
method:
P / P0
V (1 P / P0 )
A plot of vs P/P0 will yield a straight line with slope of equal to
(c-1)/(cVm) and intersect 1/(cVm).
For a given adsorption system, c and Vm are constant values, the surface area of a solid
material
* In practice, measurement of BET surface area of a solid is carried out by N 2 physisorption

at liquid N2 temperature; for N2, Am = 16.2 x 10-20 m2
10
Pore Size by Mercury Intrusion
• For materials with pore diameters greater than about 30Å, the
mecury intrusion method is preferred.
The penetration of mercury into the pores of a material is a
function of applied pressure.
• The Washburn equation: d  4 cos
P
• where d = pore diameter, nm

p = applied pressure, atm
θ= wetting or contact angle, between the mercury
and the solid is usually 130o
γ= the surface tension of the mercury, 0.48 N/m
• The mercury intrusion method:
11
XRD Analysis
• XRD is a useful technique to analyse crystallinity
• XRD can distinguish if solid is crystal,
amorphous, or partially crystal – amorphous
• Crystal refers to solid composed in 3D well –
ordered atomic pattern. Basic forms: cubic
tetragonal, orthorhombic, hexagonal,
monoclinic, rhombohedral, triclinic
• Amorphous is not in well ordered arrangement
XRD Analysis
Bragg’s Law
XRD Analysis
XRD Spectra (Example)
Affandi 2009
XRD Spectra (Example)
Thermal Characterization
• Thermogravimetric: observation of mass
change when sample is exposed with heat
(TGA)
• Thermal Differential : Observation of

temperature difference between sample and
reference upon temperature increase (DSC)
Thermogravimetric Analysis
TGA Graph
Thermal Analysis: DSC
DSC Thermograph (Example)
Spectroscopy Application
IR Spectrum
Principal Correlation Chart Region freq. (cm-1) what is found there??
OH 3600 cm -1
XH region 3800 - 2600 OH, NH, CH (sp, sp2, sp3) stretches
NH 3500 cm-1
triple bond2400 - 2000 CºC, CºN, C=C=C stretches
CH 3000 cm-1
double bond 1900 - 1500 C=O, C=N, C=C stretches
CN 2250 cm-1
CC 2150 cm-1 fingerprint 1500 - 400 many types of absorptions
C=O 1715 cm-1 1400 - 900 C-O, C-N stretches
C=C 1650 cm-1 1500 - 1300 CH in-plane bends, NH bends
CO 1100 cm-1 1000 - 650 CH out-of-plane (oop) bends
Dispersive (Double Beam) IR Split Photometer

Beam Air
Spectrophotometer
Prism
or
IR Source Lenz Diffraction Slit Sample Recorder
Grating
22
Electron Microscope
Scanning electron microscope (SEM) : images of a
sample by scanning it with a focused beam of
electrons. SEM is the most popular technique in
electron microscopy (EM) application.
Transmission electron microscopy (TEM): image is

formed from the interaction of the high voltage
electrons transmitted through the specimen in an
ultra-thin film. TEM gives higher magnification and
resolution than any other EM applications.
TEM machine lay-out
SEM diagram
SEM Images (example)
(Lawrence National Lab at Berkeley)

TEM Images (example)
(Max Planck Institute)

Dispersion or Crystallite Size of Catalytic Species
Chemisorption
• When a structure has a definite XRD pattern, it usually has less
than optimum activity. This is because most catalytic reactions
are favored by either amorphous materials or extremely small
crystallites.
• Frequently, the purpose of the preparation technique is to
disperse the catalytic components to maximize their availability
to reactants:
no. of catalytic sites on the surface  100%
% dispersion = theoretical no. of sites present
When this is done effectively, only small crystals are present
and the diffraction of X rays is minimized.
• Selective chemisorption can be used to measure the accessible
catalytic component on the surface by noting the amount of
gas adsorbed per unit weight of catalyst.
28
• One assumes that the catalytic surface area is proportional to
the number of active sites. A gas that will selectively
chemisorb only onto the metal and not the support is used
under predetermined conditions.
Hydrogen and CO are most commonly used as selective
adsorbates for many supported metals.
• The measurements are usually carried out in a static vacuum
system similar to that used for BET surface area
measurements.
• Chemisorption isotherm (monolayer coverage, 1 H per metal
site)
One can determine the catalytic surface area by multiplying
molecules adsorbed by cross-sectional area of the site and
dividing by the weight of catalyst, e.g., the cross-sectional area
of Pt is 8.9Å2 and Ni, 6.5Å2.
29
• The static vacuum technique is time-consuming. Alternatively,
a dynamic pulse technique has been used in which a pulse of
adsorbate such as H2 or CO is injected into a stream of inert
gas and passed through a bed of catalyst.
• The static method measures only species that are strongly
adsorbed.
• The dynamic method, performed under equilibrium
conditions, measures strong and weakly chemisorbed species.
Thus, static techniques usually give better dispersion results.
31
• Thanks

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• Characterization figures out catalysts properties:

• Surface area : Brunner – Emmet – Teller (BET)

• Thermal property (melting point, latent heat) :

• Molecular structure and bonds: Infra – Red

• Scanning Electron Microscopy (SEM):

Adsorption On Solid Surface

* In practice, measurement of BET surface area of a solid is carried out by N 2 physisorption

• where d = pore diameter, nm

• Thermal Differential : Observation of

Dispersive (Double Beam) IR Split Photometer

Transmission electron microscopy (TEM): image is

(Lawrence National Lab at Berkeley)

(Max Planck Institute)

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