Catalysis

Catalysis (/kəˈtæləsɪs/) is the increase in rate of a chemical reaction due to an added substance
known as a catalyst[1][2] (/ˈkætəlɪst/). Catalysts are not consumed by the reaction and remain
unchanged after it.[3] If the reaction is rapid and the catalyst recycles quickly, very small amounts of
catalyst often suffice;[4] mixing, surface area, and temperature are important factors in reaction rate.
Catalysts generally react with one or more reactants to form intermediates that subsequently give
the final reaction product, in the process of regenerating the catalyst.

A range of industrial catalysts in pellet form

An air filter that uses a low-

temperature oxidation catalyst to
convert carbon monoxide to less toxic
carbon dioxide at room temperature.
It can also remove formaldehyde from
the air.

The rate increase occurs because the catalyst allows the reaction to occur by an alternative
mechanism which may be much faster than the non-catalyzed mechanism. However the non-
catalyzed mechanism does remain possible, so that the total rate (catalyzed plus non-catalyzed)
can only increase in the presence of the catalyst and never decrease.[5]
Catalysis may be classified as either homogeneous, whose components are dispersed in the same
phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in
the same phase. Enzymes and other biocatalysts are often considered as a third category.

Catalysis is ubiquitous in chemical industry of all kinds.[6] Estimates are that 90% of all
commercially produced chemical products involve catalysts at some stage in the process of their
manufacture.[7]

The term "catalyst" is derived from Greek καταλύειν, kataluein, meaning "loosen" or "untie". The
concept of catalysis was invented by chemist Elizabeth Fulhame, based on her novel work in
oxidation-reduction experiments.[8][9]

General principles

Example

An illustrative example is the effect of catalysts to speed the decomposition of hydrogen peroxide
into water and oxygen:

2 H2 O 2 → 2 H2 O + O2

This reaction proceeds because the reaction products are more stable than the starting compound,
but this decomposition is so slow that hydrogen peroxide solutions are commercially available. In
the presence of a catalyst such as manganese dioxide this reaction proceeds much more rapidly.
This effect is readily seen by the effervescence of oxygen.[10] The catalyst is not consumed in the
reaction, and may be recovered unchanged and re-used indefinitely. Accordingly, manganese dioxide
is said to catalyze this reaction. In living organisms, this reaction is catalyzed by enzymes (proteins
that serve as catalysts) such as catalase.

Another example is the effect of catalysts on air pollution and reducing the amount of carbon
monoxide. Development of active and selective catalysts for the conversion of carbon monoxide
into desirable products is one of the most important roles of catalysts. Using catalysts for
hydrogenation of carbon monoxide helps to remove this toxic gas and also attain useful
materials.[11]

Units

The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is quantified
in moles per second. The productivity of a catalyst can be described by the turnover 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 efficiency of enzymatic
catalysis, see the article on enzymes.

Catalytic reaction mechanisms

In general, chemical reactions occur faster in the presence of a catalyst because the catalyst
provides an alternative reaction mechanism (reaction pathway) having a lower activation energy
than the non-catalyzed mechanism. In catalyzed mechanisms, the catalyst is
regenerated.[12][13][14][15]

As a simple example occurring in the gas phase, the reaction 2 SO2 + O2 → 2 SO3 can be catalyzed
by adding nitric oxide. The reaction occurs in two steps:

2 NO + O2 → 2 NO2 (rate-determining)
NO2 + SO2 → NO + SO3 (fast)

The NO catalyst is regenerated. The overall rate is the rate of the slow step[15]

v=2k1[NO]2[O2].

An example of heterogeneous catalysis is the reaction of oxygen and hydrogen on the surface of
titanium dioxide (TiO2, or titania) to produce water. Scanning tunneling microscopy showed that the
molecules undergo adsorption and dissociation. The dissociated, surface-bound O and H atoms
diffuse together. The intermediate reaction states are: HO2, H2O2, then H3O2 and the reaction
product (water molecule dimers), after which the water molecule desorbs from the catalyst
surface.[16][17]
Reaction energetics

Generic potential energy diagram showing the

effect of a catalyst in a hypothetical exothermic
chemical reaction X + Y to give Z. The presence
of the catalyst opens a different reaction
pathway (shown in red) with lower activation
energy. The final result and the overall
thermodynamics are the same.

Catalysts enable pathways that differ from the uncatalyzed reactions. These pathways have 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 the reaction rate or selectivity, or enable the reaction
at lower temperatures. This effect can be illustrated with an energy profile diagram.

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. The ratio of the forward and the reverse reaction
rates is unaffected (see also thermodynamics). The second law of thermodynamics describes why
a catalyst does not change 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 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 a 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.[18] Thus, catalysts do not alter the equilibrium constant. (A catalyst
can however change the equilibrium concentrations by reacting in a subsequent step. It is then
consumed as the reaction proceeds, and thus it is also a reactant. Illustrative is the base-catalyzed
hydrolysis of esters, where the produced carboxylic acid immediately reacts with the base catalyst
and thus the reaction equilibrium is shifted towards hydrolysis.)

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 the
transition state. It does not change the energy difference between starting materials and products
(thermodynamic barrier), or the available energy (this is provided by the environment as heat or
light).

Related concepts

Some so-called catalysts are really precatalysts. Precatalysts convert to catalysts in the reaction.
For example, Wilkinson's catalyst RhCl(PPh3)3 loses one triphenylphosphine ligand before entering
the true catalytic cycle. Precatalysts are easier to store but are easily activated in situ. Because of
this preactivation step, many catalytic reactions involve an induction period.

In cooperative catalysis, chemical species that improve catalytic activity are called cocatalysts or
promoters.

In tandem catalysis two or more different catalysts are coupled in a one-pot reaction.

In autocatalysis, the catalyst is a product of the overall reaction, in contrast to all other types of
catalysis considered in this article. The simplest example of autocatalysis is a reaction of type A + B
→ 2 B, in one or in several steps. The overall reaction is just A → B, so that B is a product. But since
B is also a reactant, it may be present in the rate equation and affect the reaction rate. As the
reaction proceeds, the concentration of B increases and can accelerate the reaction as a catalyst. In
effect, the reaction accelerates itself or is autocatalyzed. An example is the hydrolysis of an ester
such as aspirin to a carboxylic acid and an alcohol. In the absence of added acid catalysts, the
carboxylic acid product catalyzes the hydrolysis.

Switchable catalysis refers to a type of catalysis where the catalyst can be toggled between
different ground states possessing distinct reactivity, typically by applying an external stimulus.[19]
This ability to reversibly switch the catalyst allows for spatiotemporal control over catalytic activity
and selectivity. The external stimuli used to switch the catalyst can include changes in temperature,
pH, light,[20] electric fields, or the addition of chemical agents.

A true catalyst can work in tandem with a sacrificial catalyst. The true catalyst is consumed in the
elementary reaction and turned into a deactivated form. The sacrificial catalyst regenerates the true
catalyst for another cycle. The sacrificial catalyst is consumed in the reaction, and as such, it is not
really a catalyst, but a reagent. For example, osmium tetroxide (OsO4) is a good reagent for
dihydroxylation, but it is highly toxic and expensive. In Upjohn dihydroxylation, the sacrificial catalyst
N-methylmorpholine N-oxide (NMMO) regenerates OsO4, and only catalytic quantities of OsO4 are
needed.
Classification

Catalysis may be classified as either homogeneous or heterogeneous. A homogeneous catalysis is

one whose components are dispersed in the same phase (usually gaseous or liquid) as the
reactant's molecules. A heterogeneous catalysis is one where the reaction components are not in
the same phase. Enzymes and other biocatalysts are often considered as a third category. Similar
mechanistic principles apply to heterogeneous, homogeneous, and biocatalysis.

Heterogeneous catalysis

The microporous molecular structure

of the zeolite ZSM-5 is exploited in
catalysts used in refineries

Zeolites are extruded as pellets for

easy handling in catalytic reactors.

Heterogeneous catalysts act in a different phase than the reactants. Most heterogeneous catalysts
are solids that act on substrates in a liquid or gaseous reaction mixture. Important heterogeneous
catalysts include zeolites, alumina,[21] higher-order oxides, graphitic carbon, transition metal oxides,
metals such as Raney nickel for hydrogenation, and vanadium(V) oxide for oxidation of sulfur
dioxide into sulfur trioxide by the contact process.[22]

Diverse mechanisms for reactions on surfaces are known, depending on how the adsorption takes
place (Langmuir-Hinshelwood, Eley-Rideal, and Mars-van Krevelen).[23] The total surface area of a
solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger
the surface area for a given mass of particles.

A heterogeneous catalyst has active sites, which are the atoms or crystal faces where the substrate
actually binds. Active sites are atoms but are often described as a facet (edge, surface, step, etc.) of
a solid. Most of the volume but also most of the surface of a heterogeneous catalyst may be
catalytically inactive. Finding out the nature of the active site is technically challenging.

For example, the catalyst for the Haber process for the synthesis of ammonia from nitrogen and
hydrogen is often described as iron. But detailed studies and many optimizations have led to
catalysts that are mixtures of iron-potassium-calcium-aluminum-oxide.[24] The reacting gases
adsorb onto active sites on the iron particles. Once physically adsorbed, the reagents partially or
wholly dissociate and form new bonds. In this way the particularly strong triple bond in nitrogen is
broken, which would be extremely uncommon in the gas phase due to its high activation energy.
Thus, the activation energy of the overall reaction is lowered, and the rate of reaction increases.[25]
Another place where a heterogeneous catalyst is applied is in the oxidation of sulfur dioxide on
vanadium(V) oxide for the production of sulfuric acid.[22] Many heterogeneous catalysts are in fact
nanomaterials.

Heterogeneous catalysts are typically "supported", which means that the catalyst is dispersed on a
second material that enhances the effectiveness or minimizes its cost. Supports prevent or
minimize agglomeration and sintering of small catalyst particles, exposing more surface area, thus
catalysts have a higher specific activity (per gram) on support. Sometimes the support is merely a
surface on which the catalyst is spread to increase the surface area. More often, the support and
the catalyst interact, affecting the catalytic reaction. Supports can also be used in nanoparticle
synthesis by providing sites for individual molecules of catalyst to chemically bind. Supports are
porous materials with a high surface area, most commonly alumina, zeolites, or various kinds of
activated carbon. Specialized supports include silicon dioxide, titanium dioxide, calcium carbonate,
and barium sulfate.[26]

Electrocatalysts

In the context of electrochemistry, specifically 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.

Homogeneous catalysis

Homogeneous catalysts function in the same phase as the reactants. Typically homogeneous
catalysts are dissolved in a solvent with the substrates. One example of homogeneous catalysis
involves the influence of H+ on the esterification of carboxylic acids, such as the formation of
methyl acetate from acetic acid and methanol.[27] High-volume processes requiring a homogeneous
catalyst include hydroformylation, hydrosilylation, hydrocyanation. For inorganic chemists,
homogeneous catalysis is often synonymous with organometallic catalysts.[28] Many homogeneous
catalysts are however not organometallic, illustrated by the use of cobalt salts that catalyze the
oxidation of p-xylene to terephthalic acid.

Organocatalysis

Whereas transition metals sometimes attract most of the attention in the study of catalysis, small
organic molecules without metals can also exhibit catalytic properties, as is apparent from the fact
that many enzymes lack transition metals. Typically, organic catalysts require a higher loading
(amount of catalyst per unit amount of reactant, expressed in mol% amount of substance) than
transition metal(-ion)-based catalysts, but these catalysts are usually commercially available in bulk,
helping to lower costs. In the early 2000s, these organocatalysts were considered "new generation"
and are competitive to traditional metal(-ion)-containing catalysts.

Organocatalysts are supposed to operate akin to metal-free enzymes utilizing, e.g., non-covalent
interactions such as hydrogen bonding. The discipline organocatalysis is divided into the
application of covalent (e.g., proline, DMAP) and non-covalent (e.g., thiourea organocatalysis)
organocatalysts referring to the preferred catalyst-substrate binding and interaction, respectively.
The Nobel Prize in Chemistry 2021 was awarded jointly to Benjamin List and David W.C. MacMillan
"for the development of asymmetric organocatalysis."[29]

Photocatalysts

Photocatalysis is the phenomenon where the catalyst can receive light to generate an excited state
that effect redox reactions.[30] Singlet oxygen is usually produced by photocatalysis. Photocatalysts
are components of dye-sensitized solar cells.
Enzymes and biocatalysts

In biology, enzymes are protein-based catalysts in metabolism and catabolism. Most biocatalysts
are enzymes, but other non-protein-based classes of biomolecules also exhibit catalytic properties
including ribozymes, and synthetic deoxyribozymes.[31]

Biocatalysts can be thought of as an intermediate between homogeneous and heterogeneous

catalysts, although strictly speaking soluble enzymes are homogeneous catalysts and membrane-
bound enzymes are heterogeneous. Several factors affect the activity of enzymes (and other
catalysts) including temperature, pH, the concentration of enzymes, substrate, and products. A
particularly important reagent in enzymatic reactions is water, which is the product of many bond-
forming reactions and a reactant in many bond-breaking processes.

In biocatalysis, enzymes are employed to prepare many commodity chemicals including high-
fructose corn syrup and acrylamide.

Some monoclonal antibodies whose binding target is a stable molecule that resembles the
transition state of a chemical reaction can function as weak catalysts for that chemical reaction by
lowering its activation energy.[32] Such catalytic antibodies are sometimes called "abzymes".

Significance

Left: Partially caramelized cube sugar,

Right: burning cube sugar with ash as
catalyst
 0:06

A Ti-Cr-Pt tube (~40 μm long)

releases oxygen bubbles when
immersed in hydrogen peroxide (via
catalytic decomposition), forming a
micropump.[33]

Estimates are that 90% of all commercially produced chemical products involve catalysts at some
stage in the process of their manufacture. In 2005, catalytic processes generated about $900 billion
in products worldwide.[34] Catalysis is so pervasive that subareas are not readily classified. Some
areas of particular concentration are surveyed below.

Energy processing

Petroleum refining makes intensive use of catalysis for alkylation, catalytic cracking (breaking long-
chain hydrocarbons into smaller pieces), naphtha reforming and steam reforming (conversion of
hydrocarbons into synthesis gas). Even the exhaust from the burning of fossil fuels is treated via
catalysis: Catalytic converters, typically composed of platinum and rhodium, break down some of
the more harmful byproducts of automobile exhaust.

2 CO + 2 NO → 2 CO2 + N2

With regard to synthetic fuels, an old but still important process is the Fischer–Tropsch synthesis of
hydrocarbons from synthesis gas, which itself is processed via water-gas shift reactions, catalyzed
by iron. The Sabatier reaction produces methane from carbon dioxide and hydrogen. Biodiesel and
related biofuels require processing via both inorganic and biocatalysts.

Fuel cells rely on catalysts for both the anodic and cathodic reactions.

Catalytic heaters generate flameless heat from a supply of combustible fuel.

Bulk chemicals

Typical vanadium pentoxide catalyst

used in sulfuric acid production for an
intermediate reaction to convert
sulfur dioxide to sulfur trioxide.

Some of the largest-scale chemicals are produced via catalytic oxidation, often using oxygen.
Examples include nitric acid (from ammonia), sulfuric acid (from sulfur dioxide to sulfur trioxide by
the contact process), terephthalic acid from p-xylene, acrylic acid from propylene or propane and
acrylonitrile from propane and ammonia.[23]

The production of ammonia is one of the largest-scale and most energy-intensive processes. In the
Haber process nitrogen is combined with hydrogen over an iron oxide catalyst.[35] Methanol is
prepared from carbon monoxide or carbon dioxide but using copper-zinc catalysts.

Bulk polymers derived from ethylene and propylene are often prepared using Ziegler–Natta catalyst.
Polyesters, polyamides, and isocyanates are derived via acid–base catalysis.

Most carbonylation processes require metal catalysts, examples include the Monsanto acetic acid
process and hydroformylation.

Fine chemicals

Many fine chemicals are prepared via catalysis; methods include those of heavy industry as well as
more specialized processes that would be prohibitively expensive on a large scale. Examples
include the Heck reaction, and Friedel–Crafts reactions. Because most bioactive compounds are
chiral, many pharmaceuticals are produced by enantioselective catalysis (catalytic asymmetric
synthesis). (R)-1,2-Propandiol, the precursor to the antibacterial levofloxacin, can be synthesized
efficiently from hydroxyacetone by using catalysts based on BINAP-ruthenium complexes, in Noyori
asymmetric hydrogenation:[36]

Food processing

One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas)
of fats using nickel catalyst to produce margarine.[37] Many other foodstuffs are prepared via
biocatalysis (see below).

Environment

Catalysis affects the environment by increasing the efficiency of industrial processes, but catalysis
also plays a direct role in the environment. A notable example is the catalytic role of chlorine free
radicals in the breakdown of ozone. These radicals are formed by the action of ultraviolet radiation
on chlorofluorocarbons (CFCs).

Cl· + O3 → ClO· + O2
ClO· + O· → Cl· + O2

History

The term "catalyst", broadly defined as anything that increases the rate of a process, is derived from
Greek καταλύειν, meaning "to annul", or "to untie", or "to pick up". The concept of catalysis was
invented by chemist Elizabeth Fulhame and described in a 1794 book, based on her novel work in
oxidation–reduction reactions.[8][9][38] The first chemical reaction in organic chemistry that
knowingly used a catalyst was studied in 1811 by Gottlieb Kirchhoff, who discovered the acid-
catalyzed conversion of starch to glucose. The term catalysis was later used by Jöns Jakob
Berzelius in 1835[39] to describe reactions that are accelerated by substances that remain
unchanged after the reaction. Fulhame, who predated Berzelius, did work with water as opposed to
metals in her reduction experiments. Other 18th century chemists who worked in catalysis were
Eilhard Mitscherlich[40] who referred to it as contact processes, and Johann Wolfgang
Döbereiner[41][42] who spoke of contact action. He developed Döbereiner's lamp, a lighter based on
hydrogen and a platinum sponge, which became a commercial success in the 1820s that lives on
today. Humphry Davy discovered the use of platinum in catalysis.[43] In the 1880s, Wilhelm Ostwald
at Leipzig University started a systematic investigation into reactions that were catalyzed by the
presence of acids and bases, and found that chemical reactions occur at finite rates and that these
rates can be used to determine the strengths of acids and bases. For this work, Ostwald was
awarded the 1909 Nobel Prize in Chemistry.[44] Vladimir Ipatieff performed some of the earliest
industrial scale reactions, including the discovery and commercialization of oligomerization and the
development of catalysts for hydrogenation.[45]

Inhibitors, poisons, and promoters

An added substance that lowers the rate is called a reaction inhibitor if reversible and catalyst
poisons if irreversible.[1] Promoters are substances that increase the catalytic activity, even though
they are not catalysts by themselves.[46]

Inhibitors are sometimes referred to as "negative catalysts" since they decrease the reaction rate.[47]
However the term inhibitor is preferred since they do not work by introducing a reaction path with
higher activation energy; this would not lower the rate since the reaction would continue to occur by
the non-catalyzed path. Instead, they act either by deactivating catalysts or by removing reaction
intermediates such as free radicals.[47][12] In heterogeneous catalysis, coking inhibits the catalyst,
which becomes covered by polymeric side products.

The inhibitor may modify selectivity in addition to rate. For instance, in the hydrogenation of alkynes
to alkenes, a palladium (Pd) catalyst partly "poisoned" with lead(II) acetate (Pb(CH3CO2)2) can be
used (Lindlar catalyst).[48] Without the deactivation of the catalyst, the alkene produced would be
further hydrogenated to alkane.[49][50]

The inhibitor can produce this effect by, e.g., selectively poisoning only certain types of active sites.
Another mechanism is the modification of surface geometry. For instance, in hydrogenation
operations, large planes of metal surface function as sites of hydrogenolysis catalysis while sites
catalyzing hydrogenation of unsaturates are smaller. Thus, a poison that covers the surface
randomly will tend to lower the number of uncontaminated large planes but leave proportionally
smaller sites free, thus changing the hydrogenation vs. hydrogenolysis selectivity. Many other
mechanisms are also possible.

Promoters can cover up the surface to prevent the production of a mat of coke, or even actively
remove such material (e.g., rhenium on platinum in platforming). They can aid the dispersion of the
catalytic material or bind to reagents.
Prebiotic catalysis in the origin of life

Life is based on an interplay between information processing and catalytic activity carried out by
biological polymers.[51] A possible evolutionary pathway for the emergence of catalytic functions in
prebiotic information coding polymers was proposed.[51] It has also been proposed that life
emerged as an RNA-protein system in which the two components cross catalyzed the formation of
each other.[52]

See also

Chemical reaction
Substrate

Reagent

Enzyme

Product

Abzyme

Acid catalysis (includes Base catalysis)

Autocatalysis

BIG-NSE (Berlin Graduate School of Natural Sciences and Engineering)

Catalysis Science & Technology (a chemistry journal)

Catalytic resonance theory

Electrocatalyst

Environmental triggers

Enzyme catalysis

Industrial catalysts

Kelvin probe force microscope

Limiting reagent

Murburn concept

Pharmaceutic adjuvant
 Phase-boundary catalysis

Phase transfer catalyst

Photocatalysis

Ribozyme (RNA biocatalyst)

SUMO enzymes

Temperature-programmed reduction

Thermal desorption spectroscopy

Portals: Chemistry Biology

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External links

Science Aid: Catalysts (https://web.archive.org/web/20080530162951/http://scienceaid.co.uk/ch

emistry/inorganic/catalysis.html) Page for high school level science

W.A. Herrmann Technische Universität presentation (https://aci.anorg.chemie.tu-muenchen.de/w

ah/vortraege/catalysis.pdf) Archived (https://web.archive.org/web/20051028140531/http://aci.
anorg.chemie.tu-muenchen.de/wah/vortraege/catalysis.pdf) October 28, 2005, at the Wayback
Machine

Alumite Catalyst, Kameyama-Sakurai Laboratory, Japan (http://www.tuat.ac.jp/~kameyama/)

Inorganic Chemistry and Catalysis Group, Utrecht University, The Netherlands (https://inorganic-c
hemistry-and-catalysis.eu/)

Centre for Surface Chemistry and Catalysis (https://set.kuleuven.be/over-ons/brochures/internati

onal-brochure/docs/2014/hr-lea-bio-micro-surface-chem.pdf)

CarboCat Laboratory, University of Concepcion, Chile (https://sites.google.com/view/carbocatude

c)

NSF CENTC, Center for Enabling New Technologies (https://www.nsfcentc.org/) (through

catalysis)

"Bubbles turn on chemical catalysts" (https://www.sciencenews.org/article/bubbles-turn-chemica

l-catalysts) , Science News, April 6, 2009.