Heterogeneous Catalytic Reaction

Engineering
CH5050

Shelaka Gupta
Department of Chemical Engineering
Indian Institute of Technology, Hyderabad

Catalyst Characterization
TPR and XPS
Reference: Chapter 4, Concepts of Modern Catalysis and Kinetics by I. Chorkendorff, J.W. Niemantsverdriet
 What is Catalysis?

A reaction in which small quantity of a substance (a catalyst) increases the rate of a reaction
without getting consumed Itself.

Catalysis takes place in three elementary steps:

1. Adsorption
2. Reaction
3. Desorption
Multiple Length and Time Scales
Supported Particles

Metal Support combination determines:

• Morphology (Shape)
• Type of planes exposed
• No. of defects (steps, kinks etc.)
• Type of interface
• Degree of reduction
• Particle size
• Stability against sintering
• Involvement of support in reactions
 Requirement of Successful Catalyst

• How much production?

• How much is the selectivity (are there any by products) and high
conversion
• Can it be regenerated
• Lifetime
• Reproducible preparation and activation
• Thermal stability (no sintering)
• High mechanical strength
• High attrition resistance
 Aims of Catalyst Characterization

Applied research:
Distinguish between a good and bad catalyst

Fundamental research:
Want to know the structure of the catalyst under reaction conditions
in atomic details
 Catalyst Characterization

Particle Size:
Electron Microscopy Adsorbed Gases: Surface Area
Surface Composition H2 Chemisorption FTIR, DRIFT, TPD Total: BET
XPS, LEIS, Metal: H2 or CO Chemisorption
SIMS Pore Size Distribution: Hg Porosimetry
Composition Surface Composition
XPS, XANES, XRD XPS, LEIS,
ICP, AAS SIMS

Structure Degree of Reduction Morphology

XPS, EXAFS, TEM, TPR, XPS, Particles: TEM
XRD XANES Overall: SEM
Things that Matter in Supported Catalysts
Characterization Techniques are Derived From:
 In Situ or Under Vacuum

Real Catalyst Single Crystal

Reaction Conditions XRD, TP techniques, Infrared, TP Technique, STM,
Infrared and Raman, AFM
EXAFS, XANES, AFM,
Mossbauer, ESR, NMR

Vacuum XPS, SIMS, SNNS, LEIS, All surface science

RBS, TEM, SEM techniques
 Temperature Program Techniques

TPR Reduction
TPO Oxidation
TPS Sulfidation
TPD Desorption
TPRS Reaction Spectroscopy
TP-SIMS, TP-IR etc.
 Temperature Programmed Reduction

Measure H2 consumption by the catalyst as a function of temperature

Mass Spectrometer Measures composition of the gas leaving the reactor as a function of Temperature
 Thermodynamics of Reduction

Metal Oxide (p(H2O)/p(H2))eq

Ti TiO2 4x10-16
Fe Fe2O3 0.7
Rh RhO 1013

Careful removal of water is a key factor in the successful reduction of catalysts

 1
Pt
PtOx
Degree of Reduction

Nucleation: reduction by H2
• slow for non noble
• Fast for noble metals
0.5

Ni

NiO

0
Time
Metal Oxide Metal
 Example: TPR of Supported Catalyst

Temperature (0C)
 Example: TPR of Supported Catalyst
Full reduction:
Rh2O3 + 3H2 = 2Rh + 3 H2O
H2/Rh = 1.5

Fe2O3 + 3 H2 = 2 Fe + 3 H2O
H2/Fe = 1.5

Fe3O4 + 4 H2 = 3 Fe + 4 H2O
H2/Fe = 1.33

FeO + H2 = Fe + H2O

Temperature (0C)
 Example: TPR of Supported Catalyst
Full reduction:
Rh2O3 + 3H2 = 2Rh + 3 H2O
H2/Rh = 1.5

Fe2O3 + 3 H2 = 2 Fe + 3 H2O
H2/Fe = 1.5

Fe3O4 + 4 H2 = 3 Fe + 4 H2O
H2/Fe = 1.33

FeO + H2 = Fe + H2O

Reduction promotion:
Noble metal Rh assists the reduction of Fe
Rh metal nucleates fast, which enables H2 dissociation
H-atom reduce the iron oxide

Temperature (0C) Applied Catalysis, 10 (1984) 155-162

 TPR: Effect of Heating Rate

Heating rate β:

β = 17 K/min

β = 11 K/min

β = 6 K/min

J. Phys. Chem. B 2001, 105, 9778-9784

 TPR: Effect of Heating Rate

Heating rate β:

β = 17 K/min r=

β = 11 K/min

β = 6 K/min

J. Phys. Chem. B 2001, 105, 9778-9784

 TPR: Effect of Particle Size

Small
Nanoparticles
of CuO

Unsupported Large CuO particles

J. Catal. 37 (1975) 424

 TPR: Effect of Support Interaction

J. Catal. 37 (1975) 424

 Temperature Program Techniques

TPR Reduction
TPO Oxidation
TPS Sulfidation
TPD Desorption
TPRS Reaction Spectroscopy
TP-SIMS, TP-IR etc.
 TPO of Coke on Catalyst

Coke on Pt/SiO2 Coke on Al2O3

TPO is used to study the reactivity of C as well as how much amount of C is present

Catal. Today 93-95 (2004) 723

 Active Phase in Hydrotreating Catalysts

MoS2

Catalyst are prepared by sulfiding oxides with H2S/H2 Mixtures

 Temperature Programmed Sulfidation
TPS of MoO3/Al2O3

MoO3

MoOxS+MoS3

MoS2

JOURNAL OF CATALYSIS 92, 35-55 (1985)

 Temperature Programmed Techniques

TPR Temperature Programmed Reduction (oxides to metals)

TPO Temperature Programmed Oxidation (metals to oxides, study deactivation, mechanism)

TPS Sulfidation

Information on:
Reaction Temperature
Extent of reaction (degree of reduction)
Reaction Mechanism
Electrons and Ions cannot travel far…..
 Electrons and Ions cannot travel far…..

Spectroscopies based on electrons and ions of not too high energy (below few keV) are surface sensitive
and require measurement in vacuum
 Electrons in Atoms

Electron Orbital Energies (binding energies) are element specific

X-ray Photoelectron Spectroscopy (XPS)

Binding energies are:

Element specific
Sensitive to
oxidation state
electronegativity
XPS is characteristic of the surface region
X-ray Photoelectron Spectroscopy (XPS) Equipment

Standard x rays source:

MgK hν = 1253.6 eV
 X-ray Photoelectron Spectroscopy (XPS) Nomenclature

l = 0,1,2,3,4
s,p,d,f
Orbital momentum
4f7/2
n = 0,1,2,3,4
Main quantum number Total momentum

2j+1 electrons
Wide Scan XPS of Pt
 Element Specific

the freshly impregnated catalyst reveals that the Rh 3d 5/2 binding After reduction in hydrogen, the binding energy of the rhodium
energy is 310 eV, has decreased to 307.4 eV, indicative of metallic rhodium.
a value characteristic for trivalent rhodium (as in RhCl 3) Hence, XPS reveals both that rhodium is present in the catalyst
and the oxidation state in which it occurs.
 Element Specific

Pt 2+

Pt 4+

Inorg. Chem. 31 (1992) 2655-2658

 Oxidation States from Chemical Shifts

Inorg. Chem. 31 (1992) 2655-2658

 Oxidation States from Chemical Shifts

Binding energy increases with the oxidation state known as chemical shift
Inorg. Chem. 31 (1992) 2655-2658
 Chemical Shifts

XPS Binding Energy

Proportionality constant,
Charge on the atom Reference energy
Coulomb Contribution
(Pt with 0 valancy)
Charge Potential Model (Siegbahn)
 XPS Binding Energy Reflects the Electronegativity of Neighbors

R.D. van de Grampel, W. Ming, A. Gildenpfennig, W. van Gennip, J. Laven, J.W. Niemantsverdriet, H.H. Brongersma, G.
de With, R. van der Linde, Langmuir 20 (2004) 6344
 Shake Up Peaks

Shake up is prominent in XPS of oxides of Fe, Co, Ni, Cu

Shakeup Structures
Dispersion Effects
 Dispersion Effects

Applied Catalysis, 70 (1991) 53-71

 X-ray Photoelectron Spectroscopy (XPS)

XPS is among the most frequently used techniques in characterizing

catalysts
It readily provides the composition of the surface region

Reveals information on 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