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 Ada L Villa & PhD Lina M Gonzalez
February 11th, 2015
1

Introduction. Brief history of

catalysis
1836

1875

1900 - 1950

1960

1970 - 1990 Nowadays

Jns
Jacob
Berzelius
a Swedish
chemist
coined
the
word
catalysis.
He
wrote
inHC
Edinburg
New
1903:
Ammonia
oxidation
over
Ptsulfuric
leading
to
the
production
of
HNO
Noble
metal
catalysts
were
developed
for
control
de
CO,
and
NO
3
1960:
Weisz
and
Frilette
coined
the
word
shape-selective
catalysis
1964-1968:
zeolites
found
application
to
catalytic
cracking
and
Large-scale
production
of
acid
on
platinum
catalyst.
This
Philosophical Journal:
1913:
Ammonia
synthesis
over
iron
and
subsequent
development
of ammonia
emissions
from
automobiles.
Increased
emphasis
on
environmental
to
describe
the
unique
selectivity
properties
of
crystalline
molecular
hydrocracking
of
petroleum
feedstocks.
catalyst
was
developed
by
Pregrin
Philips
(British
Patent
No
6096,
The
substances
that
cause
the
decomposition
of
H
O
do
not
achieve
this
goal
by
being
2
2
synthesis
process
by
Bosch
and
Haber.
control
in into
thethe
United
States (H
and
Europe
during
1980s
andchain
1990s
incorporated
new
O2); into
each
case the
they remain
unchanged
and
sieves or
zeolites
incompounds
cracking
n-alkanes
exclusively
straight
2O and
1831).
hence
act
by means
of an
inherentof
force
whose nature
isofstill
unknown...
So long
as the nature
1920-1940:
Catalytic
processes
forvanadium
hydrogenation
COshape-selective
to methanol
orcatalysts
liquid
Later
several
and
numerous
applications
to
led
to
the
development
titania
and
zeolite
for
products.
of
the new force .remains
hidden,
will technology
help our researches
and discussions
aboutpetroleum
it if we have
hydrocarbons.
Germany
useditthis
during World
War II when
aselective
special name
for
it. cut
I hence
will
name
it theoxides
catalyticwith
force
of
the substances,
and I will
name
petroleum
processing
and
production
of
chemicals
and
fuels:
xylene
reduction
of
nitrogen
ammonia.
Catalysts
for
supplies
had
been
off.
The shape-selectivity
of zeolites
is force
based
on their
unique
decomposition
by this force catalysis.
The catalytic
is reflected
in the
capacity ability
that someto
removal
volatile
organic
hydrocarbons
(VOCs)
and
hazardous
synthesis
and
isomerization,
ethylbenzen
synthesis
and
gasoline
1936-1942:
Catalytic
cracking
over
SiO

Al
O
,
this
was
the
first
significant
use
of solid
substances
have,
by
their
mere
presence
and
not
by
their
own
reactivity,
to size
awaken
activities
2
2
3
selectively
admit
or
reject
molecules
of
characteristic
and/or
that
are slumbering
in molecules
at Very
a given
temperature.
catalysts
insuch
petroleum
industry.
important
developments
allowed refiners to
organics
as
chlorohydrocarbons
were
also developed.

???

production
methanol.
increaseat
gasoline
yield
and the
crudeWorld.mp4
more
efficiently.
shape
thefrom
entrance
to petroleum
molecular-size
pores
containing active sites.
CATALYSIS in Modern

Classification of catalyst
technologies.
Catalyst
technologies
Petroleum refining

Reaction type
- Hydrogenations.
- Oxidations.

- Synthesis.
- Polymerizations.
- Enzyme reactions.

Chemicals
manufacturing

Environmental
Clean-up
Technologies for
control of emissions
Mobile
sources

Stationary
sources
3

Definition: What is a catalysts?

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.

A catalyst changes the kinetics

of the reaction, but does not
change the thermodynamics.

Increase reaction rate (kinetics).

It does not change thermodynamic
equilibrium of the reaction.
Remains unalterable during the
reaction.
4

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
5

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 transformed to
products.
Heat of the reaction does not
change.

Rate or reaction increases

exponentially with decreasing
the activation energy, then
reduction of this increases
dramatically the reaction rate.

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.
7

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.

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.

Steps in a Heterogeneous
Catalytic Reaction.

Steps:
Steps:
Reactants

Products

7)
6)
5)
Intraparticle
Desorption:
of
diffusion:
(film
products
massof
from
1)
2)
3)
4) Bulk
Adsorption:
Surface
Bulk
diffusion.
reaction:
Adsorption
Diffusion:
involving
1)
Bulkdiffusion
diffusion:
Diffusion
transfer
Intraparticle
the
catalysts
ofofreactants
product):
diffusion
sites.
bulk
ofcatalyst
the
Diffusion
formation
reactants
or
reactants
conversion
onto
the
through
of
of
the
through
2)
Intraparticle
Diffusion.
diffusion
products
of
through
the sites).
products
the
across
the
surface
various
porous
(Active
adsorbed
network
intermediates.
ofcatalyst
the
the
stagnant
gas
film
or
3)
Adsorption
the
pores.
boundary
surrounding
catalyst
to thelayer
catalytic
surface
boundary
layer
4)
Surface
reaction
the
catalyst
particle.
(active
sites).
surrounding the catalyst
5) Desorption
particle to the external
6) Intraparticle
diffusion
catalyst surface.
7) Bulk diffusion.
10

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.
11

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:
12

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

14

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.

15

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.

16

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.
17

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.
18

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. highthroughput 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.
19

Catalyst Design
Level 3 Elucidation: The aim is to identify the fundamental building
blocks of knowledge which can be assembled to build a molecularlevel 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.

20

Combinatorial Assays
The High-Throughput Approach

21

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.
22

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.
23

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.
24

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.

25

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.

26

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.
27

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.

28

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. Furln y E. Mata. Qumica combinatoria. Volumen 21,
nmero 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 (pgs. 391-408)
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