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Catalyst redirects here. For other uses, see Catalyst carbonyl compounds, or form specic intermediates that
(disambiguation).
are not produced naturally, such as osmate esters in
Catalysis is the increase in the rate of a chemical re- osmium tetroxide-catalyzed dihydroxylation of alkenes,
or cause dissociation of reagents to reactive forms, such
as chemisorbed hydrogen in catalytic hydrogenation.
Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the frequency of
contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slowest step, and rates
are limited by amount of catalyst and its activity. In
heterogeneous catalysis, the diusion of reagents to the
surface and diusion of products from the surface can be
rate determining. A nanomaterial-based catalyst is an example of a heterogeneous catalyst. Analogous events associated with substrate binding and product dissociation
apply to homogeneous catalysts.
Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by
secondary processes. In heterogeneous catalysis, typical
An air lter that utilizes low-temperature oxidation catalyst used
secondary processes include coking where the catalyst beto convert carbon monoxide to less toxic carbon dioxide at room
comes covered by polymeric side products. Additionally,
temperature. It can also remove formaldehyde from the air.
heterogeneous catalysts can dissolve into the solution in a
solidliquid system or sublimate in a solidgas system.
action due to the participation of an additional substance
called a catalyst.[1] With a catalyst, reactions occur faster
and with less energy. Because catalysts are not consumed, they are recycled. Often only tiny amounts are 2 Background
required.[2]
Technical perspective
3 GENERAL PRINCIPLES
3
3.1
General principles
Units
Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so for the overall reaction:
X+YZ
As a catalyst is regenerated in a reaction, often only small
amounts are needed to increase the rate of the reaction.
In practice, however, catalysts are sometimes consumed
in secondary processes.
As an example of a detailed mechanism at the microscopic level, in 2008 Danish researchers rst revealed
the sequence of events when oxygen and hydrogen combine on the surface of titanium dioxide (TiO2 , or titania) to produce water. With a time-lapse series
of scanning tunneling microscopy images, they determined the molecules undergo adsorption, dissociation
and diusion before reacting. The intermediate reaction
states were: HO2 , H2 O2 , then H3 O2 and the nal reaction product (water molecule dimers), after which the water molecule desorbs from the catalyst surface.[7][8]
There are further derived SI units related to catalytic ac- in a hypothetical exothermic chemical reaction X + Y to give Z.
tivity, see the above reference for details.
The presence of the catalyst opens a dierent reaction pathway
3.2
Typical mechanism
3
the chemical equilibrium of a reaction. Suppose there
was such a catalyst that shifted an equilibrium. Introducing the catalyst to the system would result in a reaction to move to the new equilibrium, producing energy.
Production of energy is a necessary result since reactions
are spontaneous if and only if Gibbs free energy is produced, and if there is no energy barrier, there is no need
for a catalyst. Then, removing the catalyst would also result in reaction, producing energy; i.e. the addition and
its reverse process, removal, would both produce energy.
Thus, a catalyst that could change the equilibrium would
be a perpetual motion machine, a contradiction to the
laws of thermodynamics.[9]
4 Types
Catalysts can be heterogeneous or homogeneous, depending on whether a catalyst exists in the same phase as the
If a catalyst does change the equilibrium, then it must be
substrate. Biocatalysts (enzymes) are often seen as a sepconsumed as the reaction proceeds, and thus it is also a
arate group.
reactant. Illustrative is the base-catalysed hydrolysis of
esters, where the produced carboxylic acid immediately
reacts with the base catalyst and thus the reaction equi- 4.1 Heterogeneous catalysts
librium is shifted towards hydrolysis.
The SI derived unit for measuring the catalytic activity Main article: Heterogeneous catalysis
of a catalyst is the katal, which is moles per second. The Heterogeneous catalysts act in a dierent phase than 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.
The biochemical equivalent is the enzyme unit. For more
information on the eciency of enzymatic catalysis, see
the article on Enzymes.
The catalyst stabilizes the transition state more than it stabilizes the starting material. It decreases the kinetic barrier by decreasing the dierence in energy between starting material and transition state. It does not change the
energy dierence between starting materials and products (thermodynamic barrier), or the available energy
(this is provided by the environment as heat or light).
3.4
Materials
The chemical nature of catalysts is as diverse as catalysis itself, although some generalizations can be made.
Proton acids are probably the most widely used catalysts,
especially for the many reactions involving water, including hydrolysis and its reverse. Multifunctional solids often are catalytically active, e.g. zeolites, alumina, higherorder oxides, graphitic carbon, nanoparticles, nanodots,
and facets of bulk materials. Transition metals are often used to catalyze redox reactions (oxidation, hydrogenation). Examples are nickel, such as Raney nickel for
hydrogenation, and vanadium(V) oxide for oxidation of
sulfur dioxide into sulfur trioxide by the so-called contact
process. Many catalytic processes, especially those used
in organic synthesis, require late transition metals, such
as palladium, platinum, gold, ruthenium, rhodium, or
iridium.
The microporous molecular structure of the zeolite ZSM-5 is exploited in catalysts used in reneries
TYPES
4.1.1 Electrocatalysts
Main article: Electrocatalyst
In the context of electrochemistry, specically in fuel cell
engineering, various metal-containing catalysts are used
to enhance the rates of the half reactions that comprise
the fuel cell. One common type of fuel cell electrocatalyst is based upon nanoparticles of platinum that are supported on slightly larger carbon particles. When in contact with one of the electrodes in a fuel cell, this platinum
increases the rate of oxygen reduction either to water, or
to hydroxide or hydrogen peroxide.
Zeolites are extruded as pellets for easy handling in catalytic reactors.
5.2
4.3
Bulk chemicals
synthesis gas). Even the exhaust from the burning of fossil fuels is treated via catalysis: Catalytic converters, typIn biology, enzymes are protein-based catalysts in ically composed of platinum and rhodium, break down
metabolism and catabolism. Most biocatalysts are some of the more harmful byproducts of automobile exenzymes, but other non-protein-based classes of haust.
biomolecules also exhibit catalytic properties including
ribozymes, and synthetic deoxyribozymes.[13]
2 CO + 2 NO 2 CO2 + N2
Biocatalysts can be thought of as intermediate between homogeneous and heterogeneous catalysts, although strictly speaking soluble enzymes are homoge- With regard to synthetic fuels, an old but still important
neous catalysts and membrane-bound enzymes are het- process is the Fischer-Tropsch synthesis of hydrocarbons
erogeneous. Several factors aect the activity of enzymes from synthesis gas, which itself is processed via water(and other catalysts) including temperature, pH, concen- gas shift reactions, catalysed by iron. Biodiesel and retration of enzyme, substrate, and products. A particularly lated biofuels require processing via both inorganic and
important reagent in enzymatic reactions is water, which biocatalysts.
is the product of many bond-forming reactions and a reFuel cells rely on catalysts for both the anodic and caactant in many bond-breaking processes.
thodic reactions.
In biocatalysis, enzymes are employed to prepare many
Catalytic heaters generate ameless heat from a supply of
commodity chemicals including high-fructose corn syrup
combustible fuel.
and acrylamide.
Some monoclonal antibodies whose binding target is
a stable molecule which resembles the transition state
of a chemical reaction can function as weak catalysts 5.2 Bulk chemicals
for that chemical reaction by lowering its activation
energy.[14] Such catalytic antibodies are sometimes called Some of the largest-scale chemicals are produced via
catalytic oxidation, often using oxygen. Examples in"abzymes".
clude nitric acid (from ammonia), sulfuric acid (from
sulfur dioxide to sulfur trioxide by the chamber process),
terephthalic acid from p-xylene, and acrylonitrile from
5 Signicance
propane and ammonia.
Many other chemical products are generated by largescale reduction, often via hydrogenation. The largestscale example is ammonia, which is prepared via the
Haber process from nitrogen. Methanol is prepared from
carbon monoxide.
Most carbonylation processes require metal catalysts, examples include the Monsanto acetic acid process and
Estimates are that 90% of all commercially produced hydroformylation.
chemical products involve catalysts at some stage in
the process of their manufacture.[15] In 2005, catalytic processes generated about $900 billion in products
5.3 Fine chemicals
worldwide.[16] Catalysis is so pervasive that subareas are
not readily classied. Some areas of particular concenMany ne chemicals are prepared via catalysis; methods
tration are surveyed below.
include those of heavy industry as well as more specialized processes that would be prohibitively expensive on
a large scale. Examples include olen metathesis using
5.1 Energy processing
Grubbs catalyst, the Heck reaction, and Friedel-Crafts
Petroleum rening makes intensive use of catalysis reactions.
for alkylation, catalytic cracking (breaking long-chain Because most bioactive compounds are chiral, many
hydrocarbons into smaller pieces), naphtha reforming pharmaceuticals are produced by enantioselective catalyand steam reforming (conversion of hydrocarbons into sis (catalytic asymmetric synthesis).
5.4
9 SEE ALSO
Food processing
this would not reduce the rate since the reaction would
continue to occur by the non-catalyzed path. Instead they
One of the most obvious applications of catalysis is the act either by deactivating catalysts, or by removing reachydrogenation (reaction with hydrogen gas) of fats us- tion intermediates such as free radicals.[24][25]
ing nickel catalyst to produce margarine.[17] Many other
The inhibitor may modify selectivity in addition to rate.
foodstus are prepared via biocatalysis (see below).
For instance, in the reduction of acetylene to ethylene,
a palladium (Pd) catalyst partly poisoned with lead(II)
acetate (Pb(CH3 COO)2 ) can be used. Without the deac5.5 Environment
tivation of the catalyst, the ethene produced will be further reduced to ethane.[26][27]
Catalysis impacts the environment by increasing the efciency of industrial processes, but catalysis also plays The inhibitor can produce this eect by, e.g., selectively
a direct role in the environment. A notable example is poisoning only certain types of active sites. Another
the catalytic role of chlorine free radicals in the break- mechanism is the modication of surface geometry. For
down of ozone. These radicals are formed by the action instance, in hydrogenation operations, large planes of
metal surface function as sites of hydrogenolysis catalof ultraviolet radiation on chlorouorocarbons (CFCs).
ysis while sites catalyzing hydrogenation of unsaturates
History
Abzyme
Inhibitors are sometimes referred to as negative catalysts since they decrease the reaction rate.[24] However
the term inhibitor is preferred since they do not work by
introducing a reaction path with higher activation energy;
Autocatalysis
BIG-NSE (Berlin Graduate School of Natural Sciences and Engineering)
Environmental triggers
7
Enzyme catalysis
Industrial catalysts
Kelvin probe force microscope
Limiting reagent
Pharmaceutic adjuvant
Phase Boundary Catalysis
Phase transfer catalyst
Photocatalysis
Ribozyme (RNA biocatalyst)
SUMO enzymes
Temperature-programmed reduction
Thermal desorption spectroscopy
10
References
[10] Helmut Knzinger, Karl Kochloe Heterogeneous Catalysis and Solid Catalysts in Ullmanns Encyclopedia
of Industrial Chemistry 2002, Wiley-VCH, Weinheim.
doi:10.1002/14356007.a05_313. Article Online Posting
Date: January 15, 2003
[11] Arno Behr Organometallic Compounds and Homogeneous Catalysis Ullmanns Encyclopedia of
Industrial Chemistry, 2002, Wiley-VCH, Weinheim.
doi:10.1002/14356007.a18_215. Article Online Posting
Date: June 15, 2000
[12] C. Elschenbroich, Organometallics (2006) Wiley-VCH:
Weinheim. ISBN 978-3-527-29390-2
[13] D. L. Nelson and M. M. Cox Lehninger, Principles of Biochemistry 3rd Ed. Worth Publishing: New York, 2000.
ISBN 1-57259-153-6.
[14] http://www.documentroot.com/2010/03/
catalytic-antibodies-simply-explained.html
[15] Recognizing the Best in Innovation: Breakthrough Catalyst. R&D Magazine, September 2005, p. 20.
[16] 1.4.3 INDUSTRIAL PROCESS EFFICIENCY. climatetechnology.gov
[17] Types of catalysis. Chemguide. Retrieved 2008-07-09.
[18] Brd Lindstrm and Lars J. Petterson (2003) A brief history of catalysis, Cattech, 7 (4) : 130-138. Available online at: ScienceNet.
[19] J. J. Berzelius, rsberttelsen om framsteg i fysik och kemi
[Annual report on progress in physics and chemistry],
(Stockholm, Sweden: Royal Swedish Academy of Sciences, 1835). After reviewing Eilhard Mitscherlichs research on the formation of ether, Berzelius coins the word
katalys (catalysis) on page 245:
Original: Jag skall derfre, fr att begagna en i kemien vlknd hrledning, kalla
den kroppars katalytiska kraft, snderdelning
genom denna kraft katalys, likasom vi med ordet analys beteckna tskiljandet af kroppars
bestndsdelar medelst den vanliga kemiska
frndskapen.
11
Dbereiner (1823) Neu entdeckte merkwrdige
Eigenschaften des Platinsuboxyds, des oxydirten
Schwefel-Platins und des metallischen Platinstaubes (Newly discovered remarkable properties
of platinum suboxide, oxidized platinum sulde and
metallic platinum dust), Journal fr Chemie und
Physik, 38 : 321-326.
11
External links
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12.3
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