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Solid Catalysts

Catalysis Basic Principles and Catalyst Development

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A catalyst accelerates a chemical reaction.

It does so by forming bonds with the reacting molecules,

Figure 1. Every catalytic

reaction is a sequence of
elementary steps, in which
reactant molecules bind to
the catalyst, where they
react, after which the product
detaches from the catalyst,
liberating the latter for the
next cycle.

To see how the catalyst accelerates the reaction, we need to

look at the potential energy diagram

Figure 2. Potential energy diagram

of a heterogeneous catalytic
reaction, with gaseous reactants
and products and a solid catalyst.
Note that the uncatalyzed reaction
has to overcome a substantial
energy barrier, whereas the
barriers in the catalytic route are
much lower.

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The energy diagram illustrates several important points:

. The catalyst offers an alternative path for the reaction, which is obviously more
complex, but energetically much more favorable.
. The activation energy of the catalytic reaction is significantly smaller than that of
the uncatalyzed reaction; hence, the rate of the catalytic reaction is much larger.
. The overall change in free energy for the catalytic reaction equals that of the
uncatalyzed reaction. Hence, the catalyst does not affect the equilibrium constant
for the overall reaction of A + B to P. Thus, if a reaction is thermodynamically
unfavorable, a catalyst cannot change this situation. A catalyst changes the
kinetics but not the thermodynamics.
. The catalyst accelerates both the forward and the reverse reaction to the same
extent. In other words, if a catalyst accelerates the formation of the product P
from A and B, it will do the same for the decomposition of P into A and B.

There are also cases in which the combination of catalyst with

reactants or products will not be successful:
. If the bonding between reactants and catalyst is too weak, there will be hardly any
conversion of A and B into products.
. Conversely if the bond between the catalyst and one of the reactants, say A, is too
strong, the catalyst will be mostly occupied with species A, and B is not available to
form the product.
. If A and B both form strong bonds with the catalyst, the intermediate situation with A
or B on the catalyst may be so stable that reaction becomes unlikely. In terms of Fig.
2, the second level lies so deep that the activation energy to form P on the catalyst
becomes too high. The catalyst is said to be poisoned by (one of) the reactants.
. In the same way, the product P may be too strongly bound to the catalyst for
separation to occur. In this case the product poisons the catalyst.

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The hydrodesulfurization
activity of transition
metal sulfides obeys
Sabatiers principle

Catalysts Can Be Atoms, Molecules,

Enzymes and Solid Surfaces
Catalysts come in a multitude of forms, varying from atoms and
molecules to large structures such as zeolites or enzymes.
It is customary to distinguish the following three subdisciplines in
catalysis:

homogeneous,
heterogeneous and
Bio-catalysis.

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Bio-Catalysis
Schematic representation of
an enzyme-catalyzed
reaction. Enzymes often
match the shape of the
substrates they bind to, or the
transition state of the reaction
they catalyze. Enzymes are
highly efficient catalysts and
represent a great source of
inspiration for designing
technical catalysts

Heterogeneous Catalysis

Catalysts are nanomaterials and

catalysis is nanotechnology.
If we define nanotechnology as the
branch of materials science aiming to
control material properties on the
nanometer scale, then catalysis
represents a field where nanomaterials
have been applied commercially for
about a century.
Modern catalysis is preeminently
nanotechnology

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Reaction cycle and potential energy diagram for the catalytic

oxidation of CO by O2.

Why is Catalysis Important?

The chemical industry of the 20th century could not have developed to its
present status on the basis of non-catalytic, stoichiometric reactions alone.
Reactions can in general be controlled on the basis of temperature,
concentration, pressure and contact time. (?Cost, Safety, Side Reaction, etc)
Thermodynamic limitations, E.g. the conversion of N2 and H2 into ammonia
is practically impossible above 600 oC.
Without catalysts, many reactions that are common in the chemical industry
would not be possible, and many other processes would not be economical.

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Largest processes based on heterogeneous catalysis

Catalysts accelerate reactions,

enable industrially important
reactions to be carried out
efficiently under practically
attainable conditions.
Roughly 8590% of all chemical
products are made in catalytic
processes, and the percentage
is increasing steadily.

Catalysis and Green Chemistry

Catalysis Technology is called green - uses raw materials efficiently,
while formation of waste or undesirable byproducts is minimized
A good example is selective oxidation of ethylene to ethylene epoxide,
an important intermediate towards ethylene glycol (antifreeze)

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The catalytic route, more efficient, simple and clean.

Using silver, promoted by small amounts of chlorine, as the
catalyst, ethylene oxide is formed directly from
C2H4 + O2 C2H4O + CO2,
selectivity to ethylene oxide of around 90%.
Nowadays all production facilities for ethylene oxide use catalysts.

Opportunities in Catalysts Development and Manufacture

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Opportunities in Catalysts Development and Manufacture

Exhaust gas catalytic converter

The Many Length Scales of a Catalyst

Relevant length scales in catalysis, range from the subnanometre domain of the
atomic and molecular level to the macroscopic domain of an industrial reactor

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(a) Domain of (i) spectroscopy,

(ii) computational chemistry and
(iii) kinetics and mechanism on
the level of elementary reaction
steps.
journals in chemistry, physical
chemistry and physics

(b) Domain of (i) catalyst preparation, (ii)

characterization,
(iii) testing on the laboratory scale, and (iv)
mechanistic investigations.
Much academic research as well as exploratory work
in industry occurs on this scale.
Journals of catalysis

(c) Domain of shaped catalysts, in the

form of extrudates, spheres, or monoliths
on length scales varying from millimeters
to centimeters or higher. Focus of
materials science.
Typical issues of interest are porosity,
strength, and attrition resistance such
that catalysts are able to survive the
conditions inside industrial reactors.
Much of the knowledge is covered by
patents.

(d) Domain of CRE - extrinsic factors, the mass and

heat transport properties of reactants and products
through the catalyst bed are as important as the
intrinsic reactivity of the molecules reacting at the
catalytic site.
The catalysts mechanical stability, sensitivity to trace
impurities in the reactant feed, and degradation of
particles,
Literature on these aspects of catalysis is largely
found in chemical engineering journals and patents.

Time Scales in Catalysis

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Impact factors and citation half-lives for selected journals.

Historical development of kinetics in relation to catalysis. (From R.A. van Santen and
J.W. Niemantsverdriet, Chemical Kinetics and Catalysis, Plenum, New York, 1995.)

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Requirements of a Successful Catalyst

Catalysts can be metals, oxides, sulfides, carbides,
nitrides, acids, salts, virtually any type of material.
Solid catalysts also come in a multitude of forms and
can be loose particles, or small particles on a support.
The preparation of catalysts is a mixture of art and science,
but most of all much experience.
Catalysts are generally developed for a particular process, i.e.
for a certain reaction in a certain reactor under certain
conditions.

Successful catalyst have to be developed into a

material with the following properties:
. High activity per unit of volume in the eventual reactor.
. High selectivity towards the desired product at the conversion levels used in the
eventual reactor, and the lowest possible selectivity to byproducts that generate
waste problems.
. Sufficiently long life time with respect to deactivation.
. Possibility to regenerate, particularly if deactivation is fast.
. Reproducible preparation.
. Sufficient thermal stability against sintering, structural change or volatilization
inside the reaction environment (e.g. when steam is a byproduct of the reaction).
. High mechanical strength with respect to crushing (e.g. under the weight of the
catalyst bed or during the shaping process).
. High attrition resistance (resistance to mechanical wear).

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Structure of Metals, Oxides and Sulfides and

their Surfaces
Metal Structures The most important metals for catalysis are those of
the groups VIII and I-B of the periodic system.

Three crystal structures are important:

face-centered cubic (fcc: Ni, Cu, Rh, Pd, Ag, Ir, Pt, Au),
hexagonally close-packed (hcp: Co, Ru, Os) and
body centered cubic (bcc: Fe).

Unit cells of the face-centered cubic (fcc), body-centered

cubic (bcc), and hexagonally closed packed (hcp) lattices.

Crystal Planes
The structure and geometry of a surface play a dominant role with
respect to its reactivity in adsorption and catalysis.

Basal planes formed by cutting the unit cells of the

simple crystal structures.

Basal plane surface structures of the fcc and bcc lattices. The broken lines indicate atoms
in the second layer. Interatomic distances are given in terms of the lattice constant a.

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The reactivity of a surface

depends on the number of
unsaturated bonds. An
unsaturated bond being what is
left from a former bond with a
neighboring metal atom that had
to be broken to create the
surface.

Model of the fcc surface. Note that it basically consists of

a (111) surface with a step on each sixth row.

Adsorption sites on various surfaces

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Oxides and Sulfides

Bulk structures of oxides are best described by assuming that they are
made up of positive metal ions (cations) and negative O ions (anions).
Hypothetical particle of cubic MgO,
exhibiting three crystallographic
surfaces. The (100) and (110)
surfaces are nonpolar, implying that
Mg and O ions are present in equal
numbers, but the polar (111) surface
can be terminated either by Mg
cations or O anions. In practice, MgO
crystals predominantly show (100)
terminated surfaces.

The cations in transition metal oxides often occur in more than one oxidation
state. E.g. Molybdenum 6+, 5+, and 4+ oxidation states.
Oxide surfaces with the cation in the lower oxidation state are usually more
reactive than those in the highest oxidation state.
Cations at the surface possess Lewis acidity, i.e. they behave as electron
acceptors.
The oxygen ions behave as proton acceptors and are thus Brnsted bases.

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