Catalysis

Gold oxidation catalyst

Photcatalyst in the form of
nanoflower Berzelius is credited with
identifying the chemical
elements silicon, selenium,
Berzelius is credited with thorium, and cerium. Students
originating the chemical terms working in Berzelius's
"catalysis", "polymer", laboratory also discovered
"isomer" and "allotrope" lithium, and vanadium

Jöns Jacob Berzelius

Born 20 August 1779 Väversunda, Östergötland, Sweden
Died 7 August 1848 (aged 68) Stockholm, Sweden
 Estimates are that 90% of all commercially produced chemical products involve
catalysts at some stage in the process of their manufacture. [1] In 2005, catalytic
processes generated about $900 billion in products worldwide. [2]
Anything that increases the rate of a process is a "catalyst", a term derived from Greek
καταλύειν, meaning "to unite" The phrase catalyzed processes was coined by Jöns Jakob
Berzelius in 1836 to describe reactions that are accelerated by substances that remain unchanged
after the reaction.

Humphry Davy discovered the use of platinum in catalysis. Probably the most important metal in
catalysis.
Wilhelm Ostwald at Leipzig University started a systematic investigation into reactions that were
catalyzed by the presence of acids and bases; Ostwald was awarded the 1909 Nobel Prize in
Chemistry.

Other recent Noble prices in Chemistry for Catalysis:

2011 for palladium-catalyzed cross couplings in organic synthesis,
2007 for chemical processes on solid surfaces,
2005 for the development of the metathesis method in organic synthesis,
2001 for chirally catalysed oxidation and reduction reactions
1. Recognizing the Best in Innovation: Breakthrough Catalyst". R&D Magazine, September 2005, pg 20.
2. http://www.climatetechnology.gov/library/2005/tech-options/tor2005-143.pdf
1. Catalysts work by providing an (alternative) mechanism involving a different
transition state and lower activation energy. Consequently, more molecular
collisions have the energy needed to reach the transition state. Hence, catalysts
can enable reactions that would otherwise be blocked or slowed by a kinetic
barrier. The catalyst may increase reaction rate or selectivity, or enable the
reaction at lower temperatures.

2. In the catalyzed elementary reaction, catalysts do not change the extent of a

reaction: they have no effect on the chemical equilibrium of a reaction because
the rate of both the forward and the reverse reaction are both affected.

3. The productivity of a catalyst can be described by the turn over number (or
TON) and the catalytic activity by the turn over frequency (TOF), which is the TON
per time unit.

4. The catalyst stabilizes the transition state more than it stabilizes the starting
material. It decreases the kinetic barrier by decreasing the difference in energy
between starting material and transition state.
 Principles of
Catalysis

• A catalyst opens a new pathway with

a lower activation barrier for reaction
to follow.
• The Gibbs Energy of the reaction is
unchanged.
• There are no stable intermediates in
the catalytic pathway.
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“A catalyst accelerates a chemical reaction without
appearing in any of the products. An equilibrium is
equilibrated faster, but the position of the equilibrium will
not be changed”

The world market for catalysts is estimated to be more

than $ 2x109 and the total value of chemicals produced by
means of catalysis exceeds $ 1500x109
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 Heterogeneous Catalysis

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Typical catalytic materials

The chemical nature of catalysts is as diverse as catalysis itself, although some

generalizations can be made.

a.Proton acids are probably the most widely used catalysts, especially for the many
reactions involving water, including hydrolysis and its reverse.

b.Multifunctional solids often are catalytically active, e.g. zeolites, alumina, higher-
order oxides, graphitic carbon, nanoparticles, and facets of bulk materials.

c. Transition metals are often used to catalyze redox reactions. Many catalytic
processes, especially those used in organic synthesis, require so called "late
transition metals", which include palladium, platinum, gold, ruthenium, rhodium,
and iridium.

Chemical species that improve catalytic activity, without themselves being active,
are called co-catalysts or promoters.
Temperature and the Rate Constant
• The rates of chemical reactions are sensitive to temperature: most
reactions slow down at lower temperatures and speed up at higher
temperatures.

– This temperature dependence is contained in the rate constant, k.

Rate = k [A]
– Increasing the value of k increases the rate of the reaction. For many
reactions, every increase in temperature by 10°C doubles the reaction rate.

• The temperature dependence of k is given by the Arrhenius equation:

k  A exp(  Ea / RT )
Collision Theory

• Collision theory views the reaction rate as the result of particles colliding with a
certain frequency and minimum energy.
– Particles must collide in order to react, but most collisions do not result in a
reaction, either because the particles do not hit each other hard enough, or they
are turned the wrong way, etc.
– As the number of colliding reactants increases, the chances of two reactants
colliding also increases. Thus, increasing concentration increases the rate of the
reaction.
– Anything that increases the number of effective collisions increases the rate.

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For a general reaction

A + BC → AB + C

as A and BC collide, their electron clouds repel each other. The energy needed
to overcome this repulsion comes from the kinetic energy of the particles, and
is converted to the potential energy of the A---B---C complex.
Factors that Influence Effective Collisions

• Not every collision between reactant molecules leads to the formation of

a product molecule. The number of effective collisions, which actually lead
to the formation of a product molecule, depends on three factors:
– the exponential factor, f — the fraction with enough energy to react
(related to the activation energy).
– the collision frequency, Z —the number of collisions per unit of time.
– the orientation factor, p —the fraction of collisions with the correct
orientation.

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Activation Energy, Ea
• The height of the barrier is the activation
energy, Ea, and the configuration of the
atoms at the maximum potential energy is
the transition state or activated complex
(++).
– If the reactant particles collide with an
energy less than Ea, they bounce apart.
– If the collision energy is greater than Ea
(and orientation is right), there is enough
energy to overcome the repulsions, and
they react.
– In the transition state, the reactant bonds
are in the process of breaking, and the
product bonds are in the process of
forming.
– The higher Ea is, the slower the reaction
will be
Winger and Polanyi’s representation of Arrhenius model of
activation barriers to reactions
The Frequency Factor
• The exponential factor, f, is the fraction of collisions with enough energy to
react:

f  exp(  Ea / RT )
where R is the gas constant 8.314 J K-1 mol-1.

• At higher temperatures, the distribution of collision energies broadens and shifts

to higher energies, enlarging the fraction of collisions with energy greater than Ea.
This makes f a larger number.
Reaction Rate and Temperature

• The collision frequency, Z, is the number of collisions which occur in a

given unit of time.

• For a gas at room temperature and a pressure of 1 atmosphere, each

molecule undergoes about 109 collisions per second, or 1 collision every
10-9 s.

– If every collision resulted in a reaction, every gas phase reaction would

be over in 10-9 s. Most reactions are obviously much slower than this.

– For a reaction where Ea is 75 kJ/mol, at 298 K

f= 7 x 10-14 only 7 collisions in 100 trillion are energetic enough to cause
a reaction to occur!

• The collision frequency is directly proportional to the concentration of

the reactants.
Molecular Orientation

• Not all collisions with energy greater than Ea lead to a reaction: the
molecules have to be facing each other the right way when they hit each
other.
• The fraction of collisions having the right orientation is called the
orientation factor, p.
The Arrhenius Equation
• All of these factors can be combined into a single equation:

k  pZf  p exp(  Ea / RT )
• p and Z are often combined into a frequency factor, A (A = pZ); in this form,
this equation is known as
the Arrhenius equation (Svante Arrhenius, 1889):

k  A exp(  Ea / RT )
• Rearranging the Arrhenius equation,
we can obtain the form of an equation
of a line:

ln k  ln A  Ea / RT
Rate-Determining Steps
• Usually one step in a mechanism is much slower than the other
steps, and acts as a “bottleneck” for the reaction; the rate of this step
limits how fast the
overall reaction can occur, and is known as the rate determining step.

• The rate law for the rate-determining step represents the rate law
for the overall reaction.
 Overcoming unfavorable thermodynamic
(water splitting)

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H 2O  H2 + ½ O 2 G +286 kJ/mol, 2.3 eV, T = 3000 °C

HP and HT electrolysis

Solar thermal (Almeria, Spain) Hyrosol-2 (100kW)

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 Supporting catalysts Dispersion - nano

In an eight-atom cluster, all of the atoms are on the surface.

However, the dispersion, D, defined as the number of
surface atoms divided by the total number of atoms in the
cluster, declines rapidly with increasing cluster size.

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 The making of Ammonia
N2 + 3 H2  2 NH3

Nothing happens in the system without a catalyst as T raised

until 1000oC or higher. Above this temperature some H2
molecules are dissociated to H atoms.

H2  2 H (atoms)

For example at 1430oC with p(H2) = 150 atm., the partial pressure
of H atoms is ca. 0.1 % only above 3000 oC where N2 molecules
dissociates to N atoms and ammonia can be synthesized in
reasonable quantities.

N2  2 N (atoms)

The role of the catalyst in ammonia synthesis is that of making

the reaction go sufficiently fast (by facilitating the dissociation of
molecular nitrogen) so that significant rates are obtained.

Fritz Haber's successful synthesis of ammonia in 1909, capturing nitrogen from the air, brought him
fame and wealth.  In 1911, he moved to Berlin to head the Kaiser Wilhelm Institute for Physical
Chemistry and Electrochemistry.  In Berlin, he became friend with Albert Einstein.
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 Gas phase reaction
N N N + N

Catalytic reaction
N

N N

N N N N N

Energy profiles for the series of reaction steps to make ammonia

from N2 and H2 by both homogeneous gas-phase and iron-
35 catalyzed reactions. The role of the catalyst in decreasing the
energy barrier to reaction can be seen (vales are in kJ mol -1)
 Kinetic definition of catalysis

Paul J. Crutzen
Born: 3 December 1933, Amsterdam,
the Netherlands.
The Nobel Prize in Chemistry 1995

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 Hydrogenating organic
compounds in the presence of As you can also see in the figure
finely disintegrated metals The catalyst has not changed the
thermodynamics, H and therefore
G and Kp are unchanged, it only
affected the transition state.
Born: 5 November 1854, Carcassonne, France
Died: 14 August 1941, Toulouse, France
The Nobel Prize in Chemistry 1912
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 Examples of Catalysts
50 nm x 50 nm

Rh/Al2O3

5 nm
b
Au/TiO2

PtRu/CeO2

a
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 The active sites: acidity in zeolites

There is one acid hydrogen for every

tetrahedrally bonded aluminium.

These active sites are distributed uniformly

throughout the bulk and are bridging hydroxyl
groups.

These are the classic Bronsted acid sites, the

intrinsic strength of which is a function both
of the particular local environment and also
the Si/Al ratio.

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 The active sites: bi-functional catalysts

Example: the Pt/Al2O3 catalysts used in the hydroprocessing of

petrochemicals, the metal serves to dissociate H2, while the acid
support serves to catalyze the build-up of vital carbonium ion
intermediates.

H:H
methyl cyclo-propane

2-butene Pt butane
b

y
z x
c
a

40 Al3+ O2-
 The concept of “active site” is therefore very wide. Some examples of adsorbed
surface complex are showed, you can observe how reactants interacts with the
catalysts surface depending on the nature and distribution of the active sites.

A. NH3 (Lewis base) coordinately linked to Al+3 ions (Lewis acid) on Al2O3 surface.
B and C. Linear and bridge adsorption of CO on Pt.
D and E. Dissociative adsorption on Pt of H2 or ethane.
F. Dissociative adsorption of N2 on Fe.
G. Heterolytic dissociative adsorption of H2 on the ZnO surface.
H. Adsorbed complex with charge transference.
I. Adsorption of isobutene on silica alumina where the acid surface proton (σ-OH) was transferred to the
isobutene.
J and K. Possibilities of ethylene adsorption on Pt.
L. Adsorption of O2 on metal oxides with charge transference.
M. Dissociative adsorption of O2.
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 CH4
Hydrogen Production CO2
H2 O (by “Steam Reforming” (160 million tons/year)
Heat and “Water-gas Shift”)

H2 with CO and CO2 impurities

1 % of the World’s
energy production CO clean-up
CH4 and H2O
(by “Methanation”)
Pure H2

N2 Ammonia synthesis NH3

(by “Haber-Bosch”)
 Fertilizer  Food
for 2-3 billion people