Tutorial 4:

- Catalyst Preparation

Jimmy Faria (Office ME 361)

Catalytic Processes and Materials
MESA+ Institute of Nanotechnology

01/10/2018 Meeting 1
Master Course
 Learning targets
- Analyze and discuss the interplay between catalyst synthesis and physico-
chemical properties

2
 Catalyst synthesis
1. Various supports are used to prepare industrially useful catalysts. Alumina is a very
commonly used support. Alumina has so-called amphoteric properties. Please, explain:
a) what amphoteric properties are, and
b) how this allows for two approaches to prepare alumina

Precipitation from
Insoluble pH 4 to 12
AlO(OH) &
Al(OH)3

Soluble Soluble
Al3+ AlO2-
 Catalyst synthesis
2. Alumina is used in forms with high surface area or low surface area. Can you
mention an application for high surface area alumina, and one where low
surface area alumina is favoured?

High surface area applications

- Supported metals for hydrogenation reactions (Hydrotreating)
- Ethylene oxide synthesis (Ag/a-Al2O3)
- Acetylene hydrogenation (Pd/a-Al2O3)

Low surface area applications

- Methane reforming reaction

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 Catalyst synthesis
3. Pore volume impregnation is a commonly used method to functionalize
supports with active metal nanoparticles. Below you find an overview of the
surface charge of various supports in water. Please explain which precursor
salt, H2PtCl6 or Pt(NH3)4(NO3)2, is most suitable to obtain small, well
distributed particles in pores of SiO2. Is this salt similar or different to
functionalize MgO?
• For SiO2 use
Positively charged (Si- Pt(NH3)4(NO3)2 as it
OH2+) and negatively can form Pt(NH3)42+
charged (Si-OH-) and adsorb at pH > 2
surface

• For MgO use H2PtCl6

as it can form PtCl6-2
and adsorbed at pH
<12

5
 Catalyst synthesis
1. Below you find a typical text for the preparation of Fe-ZSM5. Answer the following questions

a) Why is NaOH added?

b) Write down the chemical

reactions that occur upon the
exchange with the ammonium
nitrate solution and the
following temperature
treatment at 823 K for 10 h?

c) Why is the treatment at 823K

necessary?

d) What is the function of the

template?

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 Catalyst synthesis
a) It is added to initiate hydrolysis reaction that leads to the formation of the zeolite

b)

+NH4+

-NH3

c) Removal of the catalyst template

d) The template is employed to create pores with controlled structure

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Catalytic Activity MeOH Synthesis
NO-Calcined catalyst
deactivates faster

N2-Calcined catalyst is
more resistant to
catalytic deactivation

Why?

- Coke
- Particle syntering
- Pore collapse
- Poisoning

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Surface Topology

Similar BET SA Similar Cu

and Loading and
Pore Volume Metal Surface

What is causing the fast deactivation?

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 Catalyst synthesis
Support (SBA-15) 12h Dynamic
Cu(NO3)2*3H2O vacuum drying
at 25 ºC

Zn(NO3)2*3H2O

HRTEM N2
Before After
723 K

Before After
NO/N2

G. Prieto, J. Zeˇcevi´c, Heiner Friedrich, K. P. de Jong, P. E. de

Jongh, “Towards stable catalysts by controlling collective properties of 10
supported metal nanoparticles”, Nature Materials, 12, 34-39, 2012
 Particle size distribution
Before MeOH synthesis After MeOH synthesis

Relatively
similar
particle
sizes

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 TEM - Tomography

Tilting the TEM grid 1

3D reconstruction 3D-spatial distribution
degree from -70 to
and alignment (inter-particle distances
70 degrees
in the x, y, z)

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 TEM - Tomography

NO-Calcined catalyst after reaction N2-Calcined catalyst after reaction

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TEM - Tomography
NO-Calcined catalyst after reaction N2-Calcined catalyst after reaction

The closer the particles the faster the growth

Spatial Distribution is important

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 Examples of TEM – Tomography of metal oxides

75 HAADF-STEM images of the 3D restructuring of the tomographic

mixed oxide particle taken every 2
degrees from 75° to -75° of incidence
angle.
HRTEM
T. N. Pham, Z. Lu, D. Shi, M. R. Komarneni, M. P. Ruiz, J. Faria* and
D. E. Resasco “Fine-Tuning the Acid-Base Properties of Boron-Doped
Magnesium Oxide Catalyst for Selective Aldol-Condensation”, 16
ChemCatChem 8 (2016) 3611.
 Examples of TEM – Tomography of metal clusters

C. Chen, et al. “Three-dimensional imaging of dislocations in a nanoparticle at atomic

resolution”, Nature, 496, 74-77, 2013

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