fbpx
Wikipedia

Catalysis

Catalysis (/kəˈtæləsɪs/) is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst[1][2] (/ˈkætəlɪst/). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice;[3] 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.

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. Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture.

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.[4][5]

General principles

Example

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

2 H2O2 → 2 H2O + 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.[6] 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.

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 usually reacts to form an intermediate, which then regenerates the original catalyst in the process.[7][8][9][10]

As a simple example 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[10]

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.[11][12]

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).[13] 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.[14] Thus, catalyst does 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.

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,[15] 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.[16]

Diverse mechanisms for reactions on surfaces are known, depending on how the adsorption takes place (Langmuir-Hinshelwood, Eley-Rideal, and Mars-van Krevelen).[17] 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 reaction actually occurs. Depending on the mechanism, the active site may be either a planar exposed metal surface, a crystal edge with imperfect metal valence, or a complicated combination of the two. Thus, not only 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 requires technically challenging research. Thus, empirical research for finding out new metal combinations for catalysis continues.

For example, in the Haber process, finely divided iron serves as a catalyst for the synthesis of ammonia from nitrogen and hydrogen. The reacting gases adsorb onto active sites on the iron particles. Once physically adsorbed, the reagents undergo chemisorption that results in dissociation into adsorbed atomic species, and new bonds between the resulting fragments form in part due to their closeness.[18] 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.[19] 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.[16]

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.[20]

In slurry reactions, heterogeneous catalysts can be lost by dissolving.

Many heterogeneous catalysts are in fact nanomaterials. Nanomaterial-based catalysts with enzyme-mimicking activities are collectively called as nanozymes.[21]

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.[22] High-volume processes requiring a homogeneous catalyst include hydroformylation, hydrosilylation, hydrocyanation. For inorganic chemists, homogeneous catalysis is often synonymous with organometallic catalysts.[23] 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."[24]

Photocatalysts

Photocatalysis is the phenomenon where the catalyst can receive light to generate an excited state that effect redox reactions.[25] 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.[26]

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.[27] Such catalytic antibodies are sometimes called "abzymes".

Significance

 
Left: Partially caramelized cube sugar, Right: burning cube sugar with ash as catalyst
A Ti-Cr-Pt tube (~40 μm long) releases oxygen bubbles when immersed in hydrogen peroxide (via catalytic decomposition), forming a micropump.[28]

Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture.[29] In 2005, catalytic processes generated about $900 billion in products worldwide.[30] The global demand for catalysts in 2014 was estimated at US$33.5 billion.[31] 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. 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.[32]

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.[33] Methanol is prepared from carbon monoxide or carbon dioxide but using copper-zinc catalysts.

Bulk polymers derived from ethylene and propylene are often prepared via Ziegler-Natta catalysis. 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:[34]

 

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.[35] 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.[4][5][36] 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[37] 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.[38] Other 18th century chemists who worked in catalysis were Eilhard Mitscherlich[39] who referred to it as contact processes, and Johann Wolfgang Döbereiner[40][41] 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.[42] 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.[43] Vladimir Ipatieff performed some of the earliest industrial scale reactions, including the discovery and commercialization of oligomerization and the development of catalysts for hydrogenation.[44]

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.[45]

Inhibitors are sometimes referred to as "negative catalysts" since they decrease the reaction rate.[46] 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.[46][7] 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.[47] Without the deactivation of the catalyst, the alkene produced would be further hydrogenated to alkane.[48][49]

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.

See also

References

  • IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "catalyst". doi:10.1351/goldbook.C00876
  1. ^ a b "Catalyst". IUPAC Compendium of Chemical Terminology. Oxford: Blackwell Scientific Publications. 2009. doi:10.1351/goldbook.C00876. ISBN 978-0-9678550-9-7.
  2. ^ Masel, Richard I (2001). Chemical Kinetics and Catalysis. New York: Wiley-Interscience. ISBN 0-471-24197-0.
  3. ^ Lerner, Louise (2011). "7 things you may not know about catalysis". Argonne National Laboratory.
  4. ^ a b Laidler, Keith J.; Cornish-Bowden, Athel (1997). (PDF). In Cornish-Bowden, Athel (ed.). New beer in an old bottle : Eduard Buchner and the growth of biochemical knowledge. Valencia: Universitat de Valencia. pp. 123–126. ISBN 9788437033280. Archived from the original (PDF) on January 23, 2015. Retrieved March 14, 2021.
  5. ^ a b Rayner-Canham, Marelene; Rayner-Canham, Geoffrey William (2001). Women in Chemistry: Their Changing Roles from Alchemical Times to the Mid-Twentieth Century. American Chemical Society. ISBN 978-0-8412-3522-9.
  6. ^ . University of Minnesota. March 2, 2005. Archived from the original on April 5, 2008.
  7. ^ a b Laidler, K.J. and Meiser, J.H. (1982) Physical Chemistry, Benjamin/Cummings, p. 425. ISBN 0-618-12341-5.
  8. ^ Laidler, Keith J.; Meiser, John H. (1982). Physical Chemistry. Benjamin/Cummings. pp. 424–425. ISBN 0-8053-5682-7.
  9. ^ Atkins, Peter; de Paula, Julio (2006). Atkins' Physical Chemistry (8th ed.). W.H.Freeman. p. 839. ISBN 0-7167-8759-8.
  10. ^ a b Steinfeld, Jeffrey I.; Francisco, Joseph S.; Hase, William L. (1999). Chemical Kinetics and Dynamics (2nd ed.). Prentice Hall. pp. 147–150. ISBN 0-13-737123-3. The catalyst concentration [C] appears in the rate expression, but not in the equilibrium ratio.
  11. ^ Jacoby, Mitch (February 16, 2009). "Making Water Step by Step". Chemical & Engineering News. p. 10.
  12. ^ Matthiesen J, Wendt S, Hansen JØ, Madsen GK, Lira E, Galliker P, Vestergaard EK, Schaub R, Laegsgaard E, Hammer B, Besenbacher F (2009). "Observation of All the Intermediate Steps of a Chemical Reaction on an Oxide Surface by Scanning Tunneling Microscopy". ACS Nano. 3 (3): 517–26. CiteSeerX 10.1.1.711.974. doi:10.1021/nn8008245. ISSN 1520-605X. PMID 19309169.
  13. ^ Srinivasan, Bharath (July 16, 2021). "A Guide to the Michaelis‐Menten equation: Steady state and beyond". The FEBS Journal. 289 (20): 6086–6098. doi:10.1111/febs.16124. ISSN 1742-464X. PMID 34270860.
  14. ^ Robertson, A.J.B. (1970) Catalysis of Gas Reactions by Metals. Logos Press, London.
  15. ^ Shafiq, Iqrash; Shafique, Sumeer; Akhter, Parveen; Yang, Wenshu; Hussain, Murid (June 23, 2020). "Recent developments in alumina supported hydrodesulfurization catalysts for the production of sulfur-free refinery products: A technical review". Catalysis Reviews. 64: 1–86. doi:10.1080/01614940.2020.1780824. ISSN 0161-4940.
  16. ^ a b Housecroft, Catherine E.; Sharpe, Alan G. (2005). Inorganic Chemistry (2nd ed.). Pearson Prentice-Hall. p. 805. ISBN 0130-39913-2.
  17. ^ Knözinger, Helmut and Kochloefl, Karl (2002) "Heterogeneous Catalysis and Solid Catalysts" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_313
  18. ^ "17.6: Catalysts and Catalysis". Chemistry LibreTexts. February 26, 2016. Retrieved July 8, 2022.
  19. ^ "Chemistry of Vanadium". Chemistry LibreTexts. October 3, 2013. Retrieved July 8, 2022.
  20. ^ Chadha, Utkarsh; Selvaraj, Senthil Kumaran; Ashokan, Hridya; Hariharan, Sai P.; Mathew Paul, V.; Venkatarangan, Vishal; Paramasivam, Velmurugan (February 8, 2022). "Complex Nanomaterials in Catalysis for Chemically Significant Applications: From Synthesis and Hydrocarbon Processing to Renewable Energy Applications". Advances in Materials Science and Engineering. 2022: e1552334. doi:10.1155/2022/1552334. ISSN 1687-8434.
  21. ^ Wei, Hui; Wang, Erkang (June 21, 2013). "Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes". Chemical Society Reviews. 42 (14): 6060–93. doi:10.1039/C3CS35486E. ISSN 1460-4744. PMID 23740388.
  22. ^ Behr, Arno (2002) "Organometallic Compounds and Homogeneous Catalysis" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a18_215
  23. ^ Elschenbroich, C. (2006) Organometallics. Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2
  24. ^ "The Nobel Prize in Chemistry 2021". NobelPrize.org.
  25. ^ Melchiorre, Paolo (2022). "Introduction: Photochemical Catalytic Processes". Chemical Reviews. 122 (2): 1483–1484. doi:10.1021/acs.chemrev.1c00993. PMID 35078320. S2CID 246287799.
  26. ^ Nelson, D.L. and Cox, M.M. (2000) Lehninger, Principles of Biochemistry 3rd Ed. Worth Publishing: New York. ISBN 1-57259-153-6.
  27. ^ . Documentroot.com (2010-03-06). Retrieved on 2015-11-11.
  28. ^ Solovev, Alexander A.; Sanchez, Samuel; Mei, Yongfeng; Schmidt, Oliver G. (2011). "Tunable catalytic tubular micro-pumps operating at low concentrations of hydrogen peroxide" (PDF). Physical Chemistry Chemical Physics. 13 (21): 10131–35. Bibcode:2011PCCP...1310131S. doi:10.1039/C1CP20542K. PMID 21505711. (PDF) from the original on March 28, 2019.
  29. ^ "Recognizing the Best in Innovation: Breakthrough Catalyst". R&D Magazine, September 2005, p. 20.
  30. ^ 1.4.3 Iindustrial Process Efficiency 2008-05-17 at the Wayback Machine. climatetechnology.gov
  31. ^ "Market Report: Global Catalyst Market" (2nd ed.). Acmite Market Intelligence.
  32. ^ Knözinger, Helmut; Kochloefl, Karl (2003). "Heterogeneous Catalysis and Solid Catalysts". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_313.
  33. ^ Smil, Vaclav (2004). Enriching the Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production (1st ed.). Cambridge, MA: MIT. ISBN 9780262693134.
  34. ^ Dub, Pavel A.; Gordon, John C. (2018). "The role of the metal-bound N–H functionality in Noyori-type molecular catalysts". Nature Reviews Chemistry. 2 (12): 396–408. doi:10.1038/s41570-018-0049-z. S2CID 106394152.
  35. ^ Clark, Jim (October 2013). "Types of catalysis". Chemguide.
  36. ^ Bård Lindström and Lars J. Petterson (2003) "A brief history of catalysis" Cattech, 7 (4) : 130–38.
  37. ^ Berzelius, J.J. (1835) Årsberättelsen om framsteg i fysik och kemi [Annual report on progress in physics and chemistry]. Stockholm, Sweden: Royal Swedish Academy of Sciences. After reviewing Eilhard Mitscherlich's research on the formation of ether, Berzelius coins the word katalys (catalysis) on p. 245:

    Original: Jag skall derföre, för att begagna en i kemien välkänd härledning, kalla den kroppars katalytiska kraft, sönderdelning genom denna kraft katalys, likasom vi med ordet analys beteckna åtskiljandet af kroppars beståndsdelar medelst den vanliga kemiska frändskapen.

    Translation: I shall, therefore, to employ a well-known derivation in chemistry, call [the catalytic] bodies [i.e., substances] the catalytic force and the decomposition of [other] bodies by this force catalysis, just as we signify by the word analysis the separation of the constituents of bodies by the usual chemical affinities.

  38. ^ Srinivasan, Bharath (September 27, 2020). "Words of advice: teaching enzyme kinetics". The FEBS Journal. 288 (7): 2068–2083. doi:10.1111/febs.15537. ISSN 1742-464X. PMID 32981225.
  39. ^ Mitscherlich, E. (1834). "Ueber die Aetherbildung" [On the formation of ether]. Annalen der Physik und Chemie. 31 (18): 273–82. Bibcode:1834AnP...107..273M. doi:10.1002/andp.18341071802.
  40. ^ Döbereiner (1822). "Glühendes Verbrennen des Alkohols durch verschiedene erhitzte Metalle und Metalloxyde" [Incandescent burning of alcohol by various heated metals and metal oxides]. Journal für Chemie und Physik. 34: 91–92.
  41. ^ Döbereiner (1823). "Neu entdeckte merkwürdige Eigenschaften des Platinsuboxyds, des oxydirten Schwefel-Platins und des metallischen Platinstaubes" [Newly discovered remarkable properties of platinum suboxide, oxidized platinum sulfide and metallic platinum dust]. Journal für Chemie und Physik. 38: 321–26.
  42. ^ Davy, Humphry (1817). "Some new experiments and observations on the combustion of gaseous mixtures, with an account of a method of preserving a continued light in mixtures of inflammable gases and air without flame". Philosophical Transactions of the Royal Society of London. 107: 77–85. doi:10.1098/rstl.1817.0009.
  43. ^ Roberts, M.W. (2000). "Birth of the catalytic concept (1800–1900)". Catalysis Letters. 67 (1): 1–4. doi:10.1023/A:1016622806065. S2CID 91507819.
  44. ^ Nicholas, Christopher P. (August 21, 2018). "Dehydration, Dienes, High Octane, and High Pressures: Contributions from Vladimir Nikolaevich Ipatieff, a Father of Catalysis". ACS Catalysis. 8 (9): 8531–39. doi:10.1021/acscatal.8b02310.
  45. ^ Dhara SS; Umare SS (2018). A Textbook of Engineering Chemistry. India: S. Chand Publishing. p. 66. ISBN 9789352830688.
  46. ^ a b Laidler, K.J. (1978) Physical Chemistry with Biological Applications, Benjamin/Cummings. pp. 415–17. ISBN 0-8053-5680-0.
  47. ^ Lindlar H.; Dubuis R. (2016). "Palladium Catalyst for Partial Reduction of Acetylenes". Organic Syntheses. doi:10.15227/orgsyn.046.0089.; Collective Volume, vol. 5, p. 880
  48. ^ Jencks, W.P. (1969) Catalysis in Chemistry and Enzymology McGraw-Hill, New York. ISBN 0-07-032305-4
  49. ^ Bender, Myron L; Komiyama, Makoto and Bergeron, Raymond J (1984) The Bioorganic Chemistry of Enzymatic Catalysis Wiley-Interscience, Hoboken, U.S. ISBN 0-471-05991-9

External links

  • Page for high school level science
  • W.A. Herrmann Technische Universität presentation
  • Alumite Catalyst, Kameyama-Sakurai Laboratory, Japan
  • Inorganic Chemistry and Catalysis Group, Utrecht University, The Netherlands
  • Centre for Surface Chemistry and Catalysis
  • Carbons & Catalysts Group, University of Concepcion, Chile
  • Center for Enabling New Technologies Through Catalysis, An NSF Center for Chemical Innovation, USA
  • "Bubbles turn on chemical catalysts", Science News magazine online, April 6, 2009.

catalysis, catalyst, redirects, here, other, uses, catalyst, disambiguation, stage, metabolism, catabolism, process, increasing, rate, chemical, reaction, adding, substance, known, catalyst, catalysts, consumed, reaction, remain, unchanged, after, reaction, ra. Catalyst redirects here For other uses see Catalyst disambiguation For the stage of metabolism see catabolism Catalysis k e ˈ t ae l e s ɪ s is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst 1 2 ˈ k ae t el ɪ s t Catalysts are not consumed in the reaction and remain unchanged after it If the reaction is rapid and the catalyst recycles quickly very small amounts of catalyst often suffice 3 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 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 Estimates are that 90 of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture The term catalyst is derived from Greek katalyein kataluein meaning loosen or untie The concept of catalysis was invented by chemist Elizabeth Fulhame based on her novel work in oxidation reduction experiments 4 5 Contents 1 General principles 1 1 Example 1 2 Units 1 3 Catalytic reaction mechanisms 1 4 Reaction energetics 1 5 Related concepts 1 6 Classification 2 Heterogeneous catalysis 2 1 Electrocatalysts 3 Homogeneous catalysis 3 1 Organocatalysis 3 2 Photocatalysts 3 3 Enzymes and biocatalysts 4 Significance 4 1 Energy processing 4 2 Bulk chemicals 4 3 Fine chemicals 4 4 Food processing 4 5 Environment 5 History 6 Inhibitors poisons and promoters 7 See also 8 References 9 External linksGeneral principles EditExample Edit An illustrative example is the effect of catalysts to speed the decomposition of hydrogen peroxide into water and oxygen 2 H2O2 2 H2O O2This 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 6 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 Units Edit 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 Edit Main article catalytic cycle 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 usually reacts to form an intermediate which then regenerates the original catalyst in the process 7 8 9 10 As a simple example 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 10 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 11 12 Reaction energetics Edit 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 13 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 14 Thus catalyst does 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 Edit 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 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 Edit 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 EditMain article 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 15 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 16 Diverse mechanisms for reactions on surfaces are known depending on how the adsorption takes place Langmuir Hinshelwood Eley Rideal and Mars van Krevelen 17 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 reaction actually occurs Depending on the mechanism the active site may be either a planar exposed metal surface a crystal edge with imperfect metal valence or a complicated combination of the two Thus not only 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 requires technically challenging research Thus empirical research for finding out new metal combinations for catalysis continues For example in the Haber process finely divided iron serves as a catalyst for the synthesis of ammonia from nitrogen and hydrogen The reacting gases adsorb onto active sites on the iron particles Once physically adsorbed the reagents undergo chemisorption that results in dissociation into adsorbed atomic species and new bonds between the resulting fragments form in part due to their closeness 18 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 19 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 16 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 20 In slurry reactions heterogeneous catalysts can be lost by dissolving Many heterogeneous catalysts are in fact nanomaterials Nanomaterial based catalysts with enzyme mimicking activities are collectively called as nanozymes 21 Electrocatalysts Edit Main article Electrocatalyst 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 EditMain article 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 22 High volume processes requiring a homogeneous catalyst include hydroformylation hydrosilylation hydrocyanation For inorganic chemists homogeneous catalysis is often synonymous with organometallic catalysts 23 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 Edit Main article 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 24 Photocatalysts Edit Main article Photocatalysis Photocatalysis is the phenomenon where the catalyst can receive light to generate an excited state that effect redox reactions 25 Singlet oxygen is usually produced by photocatalysis Photocatalysts are components of dye sensitized solar cells Enzymes and biocatalysts Edit Main article enzyme catalysis 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 26 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 27 Such catalytic antibodies are sometimes called abzymes Significance Edit Left Partially caramelized cube sugar Right burning cube sugar with ash as catalyst source source source source source source A Ti Cr Pt tube 40 mm long releases oxygen bubbles when immersed in hydrogen peroxide via catalytic decomposition forming a micropump 28 Estimates are that 90 of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture 29 In 2005 catalytic processes generated about 900 billion in products worldwide 30 The global demand for catalysts in 2014 was estimated at US 33 5 billion 31 Catalysis is so pervasive that subareas are not readily classified Some areas of particular concentration are surveyed below Energy processing Edit 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 N2With 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 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 Edit 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 32 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 33 Methanol is prepared from carbon monoxide or carbon dioxide but using copper zinc catalysts Bulk polymers derived from ethylene and propylene are often prepared via Ziegler Natta catalysis 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 Edit 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 34 Food processing Edit One of the most obvious applications of catalysis is the hydrogenation reaction with hydrogen gas of fats using nickel catalyst to produce margarine 35 Many other foodstuffs are prepared via biocatalysis see below Environment Edit 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 O2History EditThe term catalyst broadly defined as anything that increases the rate of a process is derived from Greek katalyein 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 4 5 36 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 Jons Jakob Berzelius in 1835 37 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 38 Other 18th century chemists who worked in catalysis were Eilhard Mitscherlich 39 who referred to it as contact processes and Johann Wolfgang Dobereiner 40 41 who spoke of contact action He developed Dobereiner 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 42 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 43 Vladimir Ipatieff performed some of the earliest industrial scale reactions including the discovery and commercialization of oligomerization and the development of catalysts for hydrogenation 44 Inhibitors poisons and promoters EditAn 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 45 Inhibitors are sometimes referred to as negative catalysts since they decrease the reaction rate 46 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 46 7 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 47 Without the deactivation of the catalyst the alkene produced would be further hydrogenated to alkane 48 49 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 See also EditPortals Chemistry Biology 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 amp 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 spectroscopyReferences EditIUPAC Compendium of Chemical Terminology 2nd ed the Gold Book 1997 Online corrected version 2006 catalyst doi 10 1351 goldbook C00876 a b Catalyst IUPAC Compendium of Chemical Terminology Oxford Blackwell Scientific Publications 2009 doi 10 1351 goldbook C00876 ISBN 978 0 9678550 9 7 Masel Richard I 2001 Chemical Kinetics and Catalysis New York Wiley Interscience ISBN 0 471 24197 0 Lerner Louise 2011 7 things you may not know about catalysis Argonne National Laboratory a b Laidler Keith J Cornish Bowden Athel 1997 Elizabeth Fulhame and the discovery of catalysis 100 years before Buchner PDF In Cornish Bowden Athel ed New beer in an old bottle Eduard Buchner and the growth of biochemical knowledge Valencia Universitat de Valencia pp 123 126 ISBN 9788437033280 Archived from the original PDF on January 23 2015 Retrieved March 14 2021 a b Rayner Canham Marelene Rayner Canham Geoffrey William 2001 Women in Chemistry Their Changing Roles from Alchemical Times to the Mid Twentieth Century American Chemical Society ISBN 978 0 8412 3522 9 Genie in a Bottle University of Minnesota March 2 2005 Archived from the original on April 5 2008 a b Laidler K J and Meiser J H 1982 Physical Chemistry Benjamin Cummings p 425 ISBN 0 618 12341 5 Laidler Keith J Meiser John H 1982 Physical Chemistry Benjamin Cummings pp 424 425 ISBN 0 8053 5682 7 Atkins Peter de Paula Julio 2006 Atkins Physical Chemistry 8th ed W H Freeman p 839 ISBN 0 7167 8759 8 a b Steinfeld Jeffrey I Francisco Joseph S Hase William L 1999 Chemical Kinetics and Dynamics 2nd ed Prentice Hall pp 147 150 ISBN 0 13 737123 3 The catalyst concentration C appears in the rate expression but not in the equilibrium ratio Jacoby Mitch February 16 2009 Making Water Step by Step Chemical amp Engineering News p 10 Matthiesen J Wendt S Hansen JO Madsen GK Lira E Galliker P Vestergaard EK Schaub R Laegsgaard E Hammer B Besenbacher F 2009 Observation of All the Intermediate Steps of a Chemical Reaction on an Oxide Surface by Scanning Tunneling Microscopy ACS Nano 3 3 517 26 CiteSeerX 10 1 1 711 974 doi 10 1021 nn8008245 ISSN 1520 605X PMID 19309169 Srinivasan Bharath July 16 2021 A Guide to the Michaelis Menten equation Steady state and beyond The FEBS Journal 289 20 6086 6098 doi 10 1111 febs 16124 ISSN 1742 464X PMID 34270860 Robertson A J B 1970 Catalysis of Gas Reactions by Metals Logos Press London Shafiq Iqrash Shafique Sumeer Akhter Parveen Yang Wenshu Hussain Murid June 23 2020 Recent developments in alumina supported hydrodesulfurization catalysts for the production of sulfur free refinery products A technical review Catalysis Reviews 64 1 86 doi 10 1080 01614940 2020 1780824 ISSN 0161 4940 a b Housecroft Catherine E Sharpe Alan G 2005 Inorganic Chemistry 2nd ed Pearson Prentice Hall p 805 ISBN 0130 39913 2 Knozinger Helmut and Kochloefl Karl 2002 Heterogeneous Catalysis and Solid Catalysts in Ullmann s Encyclopedia of Industrial Chemistry Wiley VCH Weinheim doi 10 1002 14356007 a05 313 17 6 Catalysts and Catalysis Chemistry LibreTexts February 26 2016 Retrieved July 8 2022 Chemistry of Vanadium Chemistry LibreTexts October 3 2013 Retrieved July 8 2022 Chadha Utkarsh Selvaraj Senthil Kumaran Ashokan Hridya Hariharan Sai P Mathew Paul V Venkatarangan Vishal Paramasivam Velmurugan February 8 2022 Complex Nanomaterials in Catalysis for Chemically Significant Applications From Synthesis and Hydrocarbon Processing to Renewable Energy Applications Advances in Materials Science and Engineering 2022 e1552334 doi 10 1155 2022 1552334 ISSN 1687 8434 Wei Hui Wang Erkang June 21 2013 Nanomaterials with enzyme like characteristics nanozymes next generation artificial enzymes Chemical Society Reviews 42 14 6060 93 doi 10 1039 C3CS35486E ISSN 1460 4744 PMID 23740388 Behr Arno 2002 Organometallic Compounds and Homogeneous Catalysis in Ullmann s Encyclopedia of Industrial Chemistry Wiley VCH Weinheim doi 10 1002 14356007 a18 215 Elschenbroich C 2006 Organometallics Wiley VCH Weinheim ISBN 978 3 527 29390 2 The Nobel Prize in Chemistry 2021 NobelPrize org Melchiorre Paolo 2022 Introduction Photochemical Catalytic Processes Chemical Reviews 122 2 1483 1484 doi 10 1021 acs chemrev 1c00993 PMID 35078320 S2CID 246287799 Nelson D L and Cox M M 2000 Lehninger Principles of Biochemistry 3rd Ed Worth Publishing New York ISBN 1 57259 153 6 Catalytic Antibodies Simply Explained Documentroot com 2010 03 06 Retrieved on 2015 11 11 Solovev Alexander A Sanchez Samuel Mei Yongfeng Schmidt Oliver G 2011 Tunable catalytic tubular micro pumps operating at low concentrations of hydrogen peroxide PDF Physical Chemistry Chemical Physics 13 21 10131 35 Bibcode 2011PCCP 1310131S doi 10 1039 C1CP20542K PMID 21505711 Archived PDF from the original on March 28 2019 Recognizing the Best in Innovation Breakthrough Catalyst R amp D Magazine September 2005 p 20 1 4 3 Iindustrial Process Efficiency Archived 2008 05 17 at the Wayback Machine climatetechnology gov Market Report Global Catalyst Market 2nd ed Acmite Market Intelligence Knozinger Helmut Kochloefl Karl 2003 Heterogeneous Catalysis and Solid Catalysts Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a05 313 Smil Vaclav 2004 Enriching the Earth Fritz Haber Carl Bosch and the Transformation of World Food Production 1st ed Cambridge MA MIT ISBN 9780262693134 Dub Pavel A Gordon John C 2018 The role of the metal bound N H functionality in Noyori type molecular catalysts Nature Reviews Chemistry 2 12 396 408 doi 10 1038 s41570 018 0049 z S2CID 106394152 Clark Jim October 2013 Types of catalysis Chemguide Bard Lindstrom and Lars J Petterson 2003 A brief history of catalysis Cattech 7 4 130 38 Berzelius J J 1835 Arsberattelsen om framsteg i fysik och kemi Annual report on progress in physics and chemistry Stockholm Sweden Royal Swedish Academy of Sciences After reviewing Eilhard Mitscherlich s research on the formation of ether Berzelius coins the word katalys catalysis on p 245 Original Jag skall derfore for att begagna en i kemien valkand harledning kalla den kroppars katalytiska kraft sonderdelning genom denna kraftkatalys likasom vi med ordet analys beteckna atskiljandet af kroppars bestandsdelar medelst den vanliga kemiska frandskapen Translation I shall therefore to employ a well known derivation in chemistry call the catalytic bodies i e substances the catalytic force and the decomposition of other bodies by this force catalysis just as we signify by the word analysis the separation of the constituents of bodies by the usual chemical affinities Srinivasan Bharath September 27 2020 Words of advice teaching enzyme kinetics The FEBS Journal 288 7 2068 2083 doi 10 1111 febs 15537 ISSN 1742 464X PMID 32981225 Mitscherlich E 1834 Ueber die Aetherbildung On the formation of ether Annalen der Physik und Chemie 31 18 273 82 Bibcode 1834AnP 107 273M doi 10 1002 andp 18341071802 Dobereiner 1822 Gluhendes Verbrennen des Alkohols durch verschiedene erhitzte Metalle und Metalloxyde Incandescent burning of alcohol by various heated metals and metal oxides Journal fur Chemie und Physik 34 91 92 Dobereiner 1823 Neu entdeckte merkwurdige Eigenschaften des Platinsuboxyds des oxydirten Schwefel Platins und des metallischen Platinstaubes Newly discovered remarkable properties of platinum suboxide oxidized platinum sulfide and metallic platinum dust Journal fur Chemie und Physik 38 321 26 Davy Humphry 1817 Some new experiments and observations on the combustion of gaseous mixtures with an account of a method of preserving a continued light in mixtures of inflammable gases and air without flame Philosophical Transactions of the Royal Society of London 107 77 85 doi 10 1098 rstl 1817 0009 Roberts M W 2000 Birth of the catalytic concept 1800 1900 Catalysis Letters 67 1 1 4 doi 10 1023 A 1016622806065 S2CID 91507819 Nicholas Christopher P August 21 2018 Dehydration Dienes High Octane and High Pressures Contributions from Vladimir Nikolaevich Ipatieff a Father of Catalysis ACS Catalysis 8 9 8531 39 doi 10 1021 acscatal 8b02310 Dhara SS Umare SS 2018 A Textbook of Engineering Chemistry India S Chand Publishing p 66 ISBN 9789352830688 a b Laidler K J 1978 Physical Chemistry with Biological Applications Benjamin Cummings pp 415 17 ISBN 0 8053 5680 0 Lindlar H Dubuis R 2016 Palladium Catalyst for Partial Reduction of Acetylenes Organic Syntheses doi 10 15227 orgsyn 046 0089 Collective Volume vol 5 p 880 Jencks W P 1969 Catalysis in Chemistry and Enzymology McGraw Hill New York ISBN 0 07 032305 4 Bender Myron L Komiyama Makoto and Bergeron Raymond J 1984 The Bioorganic Chemistry of Enzymatic Catalysis Wiley Interscience Hoboken U S ISBN 0 471 05991 9External links Edit Look up catalysis in Wiktionary the free dictionary Wikimedia Commons has media related to Catalysis Wikisource has the text of the 1911 Encyclopaedia Britannica article Catalysis Science Aid Catalysts Page for high school level science W A Herrmann Technische Universitat presentation Alumite Catalyst Kameyama Sakurai Laboratory Japan Inorganic Chemistry and Catalysis Group Utrecht University The Netherlands Centre for Surface Chemistry and Catalysis Carbons amp Catalysts Group University of Concepcion Chile Center for Enabling New Technologies Through Catalysis An NSF Center for Chemical Innovation USA Bubbles turn on chemical catalysts Science News magazine online April 6 2009 Retrieved from https en wikipedia org w index php title Catalysis amp oldid 1140615661, wikipedia, wiki, book, books, library,

article

, read, download, free, free download, mp3, video, mp4, 3gp, jpg, jpeg, gif, png, picture, music, song, movie, book, game, games.