Universidad de Antioquia

Preparation of catalysts.
Chapter 1: Methods of synthesis of catalysts
University of Antioquia
Environmental catalysis Group
Present by: Manuel J Cano
Professors: PhD Aída L Villa & PhD Lina M Gonzalez
February 11th, 2015
1
 Introduction. Brief history
of catalysis
1836 1875 1900 - 1950 1960 1970 - 1990 Nowadays

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efficiently. 2
 Classification of catalyst
technologies.
Catalyst
technologies

Petroleum refining Chemicals Environmental

manufacturing Clean-up

Reaction type
- Hydrogenations.
Technologies for
control of emissions
- Oxidations.
- Synthesis.
Mobile Stationary
- Polymerizations.
sources sources
- Enzyme reactions. 3
 Definition: What is a
catalysts?
• A catalyst changes the kinetics
of the reaction, but does not
change the thermodynamics.
• Catalyst is a material that converts
reactants into products, through a
series of elementary steps, in
which the catalyst participates
while being regenerates to its
original form at the end of each
cycle during its lifetime.
• Increase reaction rate (kinetics).
• It does not change thermodynamic
equilibrium of the reaction.
• Remains unalterable during the
reaction.
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 Example: Three Way Catalyst for
Automobile emission control.
• The internal combustion engine in automobiles combusts a gasoline/air mixture to
generate heat that is converted to mechanical work in the engine.

• The combustion process is not 100% efficient, there are some undesired by
products: CO, HC (unburned hydrocarbons), NOx (NO, NO2, N2O), CO2, H2O.
• How_Car_Exhaust_System_Works.mp4
• Three-way_catalytic_converter-Basf.mp4
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 Catalysts and Activation
Energy.
• The catalyst reduce the energy
barrier or activation energy
necessary for electron exchange
between the reactants and
products.
• The catalyst lowers the activation
barrier by providing a surface or
site for adsorption and
dissociation of the reactants, in
which they are more readily • Rate or reaction increases
transformed to products. exponentially with decreasing
the activation energy, then
• Heat of the reaction does not reduction of this increases
change. dramatically the reaction rate. 6
 Heterogeneous catalysis
• Heterogeneous catalysis is the processes whereby reactants absorb onto the
surface of a solid catalyst, are activated by chemical interaction with the catalyst
surface and selectively transformed to adsorbed products, which desorb from
the catalytic surface.
• Numerous industrial applications: chemical, food, pharmaceutical, etc. It has
been estimated that 90% of all chemical processes use heterogeneous catalysts.
• Principles of heterogeneous catalysts are complex because is a highly
interdisciplinary field and require the cooperation between chemist and
physicists, between surface scientists and reaction engineers, between theorists
and experimentalists, between spectroscopists and kineticists and between
materials scientists involved with catalyst synthesis and characterizations.

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 Heterogeneous Catalysts

• Main advantage: the catalyst being a solid material, it is easy to

separate from the gas and/or liquid reactants and product of the
overall catalytic reaction.

• Heterogeneous catalyst involves:

- Active sites (or active centers)
- The surface of the solid, typically a high-surface area material (10 – 1000
m2/g)
- It is desirable maximize the number of active sites per reactor volume.

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 Heterogeneous Catalysts

• Reaction intermediates: They are transitory and highly reactive

species that are chemically identifiable. Examples: atoms, radicals,
ions and molecules in excited states.
• Identify the reaction intermediates – and hence the mechanism – for
a heterogeneous catalytic reaction is often difficult, because many of
these intermediates are difficult to detect using conventional
methods (e.g., gas chromatography or mass spectrometry) because
they do not desorb as significant rates from the surface of the
catalyst.

9
 Steps in a Heterogeneous
Catalytic Reaction.

Steps:
Steps:

Reactants
1)
7)
6)
5)
1)
2)
3) Bulkdiffusion
4) Bulk diffusion:
Intraparticle
Desorption:
Adsorption:
Surface
Bulk diffusion. of
reaction: Diffusion
diffusion:
(film
products
massof
Adsorption
Diffusion:
involvingfrom
transfer
Intraparticle
the
2) catalysts
Diffusion
formation ofofreactants
reactants
of the product):
or
Intraparticle diffusion
sites.
reactants
conversion
onto thebulk
ofcatalyst
the
through
of
through
Diffusion.
diffusion
products
the
surface
various
porous
the of
through
(Activethe sites).
adsorbed products
network
stagnant the ofcatalyst
across
intermediates.
gas the
film or
3)
the Adsorption
pores.boundary
catalyst to thelayer surrounding
catalytic surface
4)
the boundary
Surface
catalyst
(active sites). layer
reaction
particle.
surrounding the catalyst
5) Desorption
Products
particle to the external
6) Intraparticle
catalyst surface. diffusion
7) Bulk diffusion.

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 Catalyst Characteristics

• The suitability of a catalyst for an industrial process depends mainly on the

following three properties:
- Activity: is a measure of how fast one or more reactions proceed in the
presence of the catalyst. Activity can be defined in terms of kinetics
(reaction rate), turnover number (which originates from the field of
enzymatic catalysis) and turnover frequency to quantify the specific activity
of a catalytic center for a special reaction under defined reaction conditions.
- Selectivity: is the fraction of the starting material that is converted to the
desired product P.
- Stability (deactivation behavior): Chemical, thermal and mechanical
stability of a catalyst determines its lifetime in industrial reactors.
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 Reaction rate (r).
• The specific reaction rate for a stoichiometric catalytic reaction is
formally defined as:
Volume, weight or surface
area or the catalyst.
Stoichiometric coefficient in the
stoichiometric reaction.
Number of moles of each species.
• The number of moles of species I at any point in time is defined by:

• Conversion:
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 Reaction rate dependence of
temperature and reactant
concentrations.
• The rate equation is generally approximated as a product of a function of
temperature and concentration:

• k(T) is the rate constant described by the Arrhenius law as:

A catalystofincreases
• Frequency
Fraction factor isthe
collisions thatrate and hence
proportional
results into thethe
reaction.rate constant
number by increasing
of collisions, which
A might
(providing
lead catalytic
to reactionsites)
andand/or
in the decreasing the activation
case of a catalytic reactionenergy
to the
(hence increasing
concentration ofthe fraction
catalytic of collisions resulting in reaction.
sites.

13
 Definition: Turnover
Frequency (TOF)
• TOF is a specific reaction rate based on number of active sites. Represents the
frequency at which molecules react on an active site under specific reaction
conditions.
• It is the number of molecular reactions (catalytic cycles) occurring at the
center per unit time.
• TOF must be defined at specified conditions of temperature, concentration of
reactants, and conversion. It must be measured in the absence of heat and
mass transport limitations and pore diffusional restrictions.
• Industrial applications TOF range from 10-2 – 102 s.
• In principle, the TOF is a constant for a given metal, metal oxide, or metal
sulfide in a given reaction at specified reaction conditions.

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 Turnover Number (TON)

• TON specifies the maximum use that can be made of a catalyst for a
special reaction under defined conditions by a number of molecular
reactions or reactions cycles occurring at the reactive center up to the
decay of activity.

• For industrial applications the TON is in the range of 106 – 107.

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 Selectivity
• The selectivity of a reaction is the fraction of the starting material that is
converted to the desired product P. It is expressed by the ratio of the
amount of desired product to the reacted quantity of a reaction partner A
and therefore gives information about the course of the reaction. In addition
to the desired reaction, parallel and sequential reaction can also occur.

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 Stability

• The chemical, thermal and mechanical stability of a catalyst determines its

lifetime in industrial reactors. The catalysts deactivation can be followed
by measuring activity or selectivity as a functions of time.
• Causes for catalyst deactivation includes:
- Decomposition.
- Coking.
- Poisoning.
- Sintering.
- Phase changes.
• Catalyst that lose activity during a process can often be regenerated before
they ultimately have to be replaced. The total catalyst lifetime is of crucial
importance for the economics of a process.
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 Key attributes of a good
catalyst

• Good selectivity for production of the desired products and minimal

production of undesirable byproducts.
• It should achieve adequate rates of reaction at the desired reaction
conditions of the process. (Achieve good selectivity is usually more
important than archiving high catalytic activity)
• Stability: the catalyst should show stable performance at reaction conditions
for long period of time, or it should be possible to regenerate good catalyst
performance by appropriate treatment of the desactivated catalyst after
short periods.
• It should have good accessibility of reactants and products to the active sites
such that high rates can be achieved per reactor volume.
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 Catalyst Design

• Level 1 synthesis of materials: All studies of heterogeneous catalysis

begin at the Materials Level. High-surface area catalytic materials must
be synthetized with specific structures and textures. Characterizations
studies are needed for determine the structures, compositions and
textures of the materials that have been prepared.
• Level 2 Quantification of catalyst performance: These studies can be
carried out over a wide range of catalytic materials (e.g. high-
throughput studies) to identify promising catalysts and reaction
conditions for further studies. It is necessary determine catalytic
activity, selectivity and stability with respect time-on-stream for various
reaction conditions.
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 Catalyst Design

• Level 3 Elucidation: The aim is to identify the fundamental building

blocks of knowledge which can be assembled to build a molecular-
level understanding of catalyst performance in order to guide further
investigations to improve catalyst performance. At this level is needed
to determine the surface composition and nature of the surface sites
on the catalyst.

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 Combinatorial Assays
The High-Throughput Approach

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 Combinatorial Chemistry
The High-Throughput Approach
• When new active solids are developed empirically, by trial-and-error
procedure is highly speculative and leads to a very slow rate of discovery
for the industry in question. This research strategy based on exhaustive
studies and complete understanding is also very time-consuming.
• Because of this, new research strategies have to be developed in order to
produce advances and revitalize the field of chemical research.
• Concepts of combinatorial chemistry were originally developed for the
synthesis of small organic molecules. If a family of molecules has a
common core structure, normally termed “scaffold”, bearing different
functional groups, which can varied independently of each other, then a
large number of different molecules can be generated based on this
common scaffold, following combinatorial principles.
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 Combinatorial Chemistry
The High-Throughput Approach

• HT experimentation in drug discovery and medical chemistry is widely

applied and mature approach from which combinatorial catalysis has taken
and adapted most of its experimental and software tools.
• However the proper descriptions of solid catalysts and the quantum chemical
properties are very complex and are still in their infancy, especially when
compared with the available chemoinformatics software for virtual screening
of drug candidate molecules.
• Molecular descriptors used in the pharmaceutical chemistry are variables
that represent the physiochemical properties of a class for compounds and
they are commonly classified into four types: Constitutional, topological,
geometrical and quantum chemical properties.
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 Combinatorial Chemistry
The High-Throughput Approach
• However, for solids, the situation is much more difficult than for
molecules. While for well-defined reaction steps, the product of an organic
synthetic sequence is generally also well defined; this is not necessarily
true for solids.
• The particle sizes may differ, the crystallinity can be dependent on
treatment temperature, certain phases may need different temperature to
form at differen levels of composition, different precursors will have
different reactivities, and so on.
• A simple combinatorial synthesis of complex oxides is therefore not
straightforward, and the situation is made even more complicated by the
fact that synthesis planning for solids synthesis is only in its infancy.

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 Combinatorial Chemistry
The High-Throughput Approach

• It is a pragmatic alternative.
• It is based on the fast and systematic screening of libraries of diverse
samples.
• The main idea is screening techniques used in HT methods, dozens or
even hundred of experiments involving many variables can be
performed at once. Two questions arise from this:
- Which experiments are the most relevant to carry out?
- What is the most efficient screening strategy?

• Quantitative structure-property relationship (QSPR) models.

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 Combinatorial Chemistry
The High-Throughput Approach

• The use of fundamental descriptors is very limited, since

heterogenous catalysts are complex systems, with heterogeneous
multicomponent active sites and unpredictable metastable structures.
• Tabulate information corresponding to tabulated attributes of the
starting elements/oxides making up the catalyst is an useful tool.
• A good selection of the tabulated attributes that could have an impact
in the performance and a good predictive model using neural
networks and classification trees may achieved good results.

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 Quantitative structure-property
relationship (QSPR) models.
Space A Space B Space C

• If a direct relationship is found between the catalysts (Space A), the

molecular descriptors (space B), and the figures of performance (space C), it
becomes theoretically possible to backtrack from space C to space A.
• The identification of a good catalyst according to the appropriate positions
in spaces B and C should enable the selection of structures in space A.
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 Quantitative structure-property
relationship for predictive models in
catalysis.

• Spectral data can be used together with synthesis and theoretical data as
input descriptors for catalytic QSPR modeling. Spectral descriptors can be
obtained automatically by processing of the raw characterization data.
• The QSPR model is obtained by different data-mining techniques can be
used i) as a predictive model and ii) for extraction of rules and
relationships between variables, gaining knowledge about catalysis.
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 References

1. R. Farrauto, C. Bartholomew. Fundamentals of industrial catalytic

processes. 1a ed. London: Blackie, 1997
2. G. Ertl, H. Knozinger, F. Schuth, J. Weitkamp. Handbook of
Heterogeneous Catalysis 2008. Wiley-VCH Verlag GmbH & Co. KGaA. 
3. C. Barbero, R. Furlán y E. Mata. Química combinatoria. Volumen 21,
número 124 (2011) 39-45.
4. J. Hagen, Industrial Catalysis, 2 nd. 2006.
5. Schuth , F., & Schunk, S. (2006). Combinatorial Approaches to Design
Complex Metal Oxides. En J. Fierro, Metal Oxides. Chemistry and
Applications (págs. 391-408)
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