Catalysis

Solid heterogeneous catalysts such as in automobile catalytic converters are plated on structures designed to maximize their surface area.
A low-temperature oxidation catalyst used to convert carbon monoxide to non-toxic carbon dioxide at room temperature. It can also remove formaldehyde from the air.

Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transformations. Catalysts that speed the reaction are called positive catalysts. Catalysts that slow the reaction are called negative catalysts, or inhibitors. Substances that increase the activity of catalysts are called promoters, and substances that deactivate catalysts are called catalytic poisons.

Catalytic reactions have a lower rate-limiting free energy of activation than the corresponding uncatalyzed reaction, resulting in higher reaction rate at the same temperature. However, the mechanistic explanation of catalysis is complex. Catalysts may affect the reaction environment favorably, or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds, or form specific intermediates that are not produced naturally, such as osmate esters in osmium tetroxide-catalyzed dihydroxylation of alkenes, or cause lysis of reagents to reactive forms, such as atomic hydrogen in catalytic hydrogenation.

Kinetically, catalytic reactions are typical chemical reactions, i.e. the reaction rate depends on the frequency of contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slow step, and rates are limited by amount of catalyst and its "activity". In heterogeneous catalysis, the diffusion of reagents to the surface and diffusion of products from the surface can be rate determining. Analogous events associated with substrate binding and product dissociation apply to homogeneous catalysts.

Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated or destroyed by secondary processes. In heterogeneous catalysis, typical secondary processes include coking where the catalyst becomes covered by polymeric side products. Additionally, heterogeneous catalysts can dissolve into the solution in a solid-liquid system or evaporate in a solid-gas system.

Contents

Background

The production of most industrially important chemicals involves catalysis. Similarly, most biochemically significant processes are catalysed. Research into catalysis is a major field in applied science and involves many areas of chemistry, notably in organometallic chemistry and materials science. Catalysis is relevant to many aspects of environmental science, e.g. the catalytic converter in automobiles and the dynamics of the ozone hole. Catalytic reactions are preferred in environmentally friendly green chemistry due to the reduced amount of waste generated,[1] as opposed to stoichiometric reactions in which all reactants are consumed and more side products are formed. The most common catalyst is the proton (H+). Many transition metals and transition metal complexes are used in catalysis as well. Catalysts called enzymes are important in biology.

A catalyst works by providing an alternative reaction pathway to the reaction product. The rate of the reaction is increased as this alternative route has a lower activation energy than the reaction route not mediated by the catalyst. The disproportionation of hydrogen peroxide to give water and oxygen is a reaction that is strongly affected by catalysts:

2 H2O2 → 2 H2O + O2

This reaction is favoured in the sense that reaction products are more stable than the starting material, however the uncatalysed reaction is slow. The decomposition of hydrogen peroxide is in fact so slow that hydrogen peroxide solutions are commercially available. Upon the addition of a small amount of manganese dioxide, the hydrogen peroxide rapidly reacts according to the above equation. This effect is readily seen by the effervescence of oxygen.[2] The manganese dioxide may be recovered unchanged, and re-used indefinitely, and thus is not consumed in the reaction. Accordingly, manganese dioxide catalyses this reaction.[3]

General principles of catalysis

Typical mechanism

Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process regenerating the catalyst. The following is a typical reaction scheme, where C represents the catalyst, X and Y are reactants, and Z is the product of the reaction of X and Y:

X + C → XC (1)
Y + XC → XYC (2)
XYC → CZ (3)
CZ → C + Z (4)

Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so for the overall reaction:

X + Y → Z

As a catalyst is regenerated in a reaction, often only small amounts are needed to increase the rate of the reaction. In practice, however, catalysts are sometimes consumed in secondary processes.

As an example of this process, in 2008 Danish researchers first revealed the sequence of events when oxygen and hydrogen combine on the surface of titanium dioxide (TiO2, or titania) to produce water. With a time-lapse series of scanning tunneling microscopy images, they determined the molecules undergo adsorption, dissociation and diffusion before reacting. The intermediate reaction states were: HO2, H2O2, then H3O2 and the final reaction product (water molecule dimers), after which the water molecule desorbs from the catalyst surface.[4]

Catalysis and 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 a lower activation energy. The final result and the overall thermodynamics are the same.

Catalysts work by providing an (alternative) mechanism involving a different transition state and lower activation energy. Consequently, more molecular collisions have the energy needed to reach the transition state. Hence, catalysts can enable reactions that would otherwise be blocked or slowed by a kinetic barrier. The catalyst may increase reaction rate or selectivity, or enable the reaction at lower temperatures. This effect can be illustrated with a Boltzmann distribution and 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 because the rate of both the forward and the reverse reaction are both affected (see also thermodynamics). The fact that a catalyst does not change the equilibrium is a consequence of the second law of thermodynamics. Suppose there was such a catalyst that shifted an equilibrium. Introducing the catalyst to the system would result in reaction to move to the new equilibrium, producing energy. Production of energy is a necessary result since reactions are spontaneous if and only if Gibbs free energy is produced, and if there is no energy barrier, there is no need for a catalyst. Then, removing the catalyst would also result in reaction, producing energy; i.e. the addition and its reverse process, removal, would both produce energy. Thus, a catalyst that could change the equilibrium would be a perpetual motion machine, a contradiction to the laws of thermodynamics.[5]

If a catalyst does change the equilibrium, then it must be consumed as the reaction proceeds, and thus it is also a reactant. Illustrative is the base-catalysed hydrolysis of esters, where the produced carboxylic acid immediately reacts with the base catalyst and thus the reaction equilibrium is shifted towards hydrolysis.

The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is moles per second. The activity of a catalyst can also be described by the turn over number (or TON) and the catalytic efficiency by the turn over frequency (TOF). The biochemical equivalent is the enzyme unit. For more information on the efficiency of enzymatic catalysis, see the article on Enzymes.

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

Typical catalytic materials

The chemical nature of catalysts is as diverse as catalysis itself, although some generalizations can be made. Proton acids are probably the most widely used catalysts, especially for the many reactions involving water, including hydrolysis and its reverse. Multifunctional solids often are catalytically active, e.g. zeolites, alumina and certain forms of graphitic carbon. Transition metals are often used to catalyse redox reactions (oxidation, hydrogenation). Many catalytic processes, especially those involving hydrogen, require platinum metals.

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.

Chemical species that improve catalytic activity are called co-catalysts (cocatalysts) or promotors in cooperative catalysis.

Types of catalysis

Catalysts can be either heterogeneous or homogeneous, depending on whether a catalyst exists in the same phase as the substrate. Biocatalysts are often seen as a separate group.

Heterogeneous catalysts

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. Diverse mechanisms for reactions on surfaces are known, depending on how the adsorption takes place (Langmuir-Hinshelwood, Eley-Rideal, and Mars-van Krevelen).[6] The total surface area of 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.

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 adsorbed, the bonds within the reacting molecules are weakened, and new bonds between the resulting fragments form in part due to their close proximity. In this way the particularly strong triple bond in nitrogen is weakened and the hydrogen and nitrogen atoms combine faster than would be the case in the gas phase, so the rate of reaction increases.

Heterogeneous catalysts are typically “supported,” which means that the catalyst is dispersed on a second material that enhances the effectiveness or minimizes their cost. 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 are porous materials with a high surface area, most commonly alumina or various kinds of carbon. Specialized supports include silicon dioxide, titanium dioxide, calcium carbonate, and barium sulfate.

Homogeneous catalysts

Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles invoked in heterogeneous catalysis are generally applicable. 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 esters, e.g. methyl acetate from acetic acid and methanol.[7] For inorganic chemists, homogeneous catalysis is often synonymous with organometallic catalysts.[8]

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 to water, either to hydroxide or hydrogen peroxide.

Organocatalysis

Whereas transition metals sometimes attract most of the attention in the study of catalysis, 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 (or amount of catalyst per unit amount of reactant) than transition metal-based catalysts, but these catalysts are usually commercially available in bulk, helping to reduce costs. In the early 2000s, organocatalysts were considered "new generation" and are competitive to traditional metal-containing catalysts. Enzymatic reactions operate via the principles of organic catalysis.

Significance of catalysis

Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process of their manufacture.[9] In 2005, catalytic processes generated about $900 billion in products worldwide.[10] 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, catalysed 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.

Bulk chemicals

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 chamber process), terephthalic acid from p-xylene, and acrylonitrile from propane and ammonia.

Many other chemical products are generated by large-scale reduction, often via hydrogenation. The largest-scale example is ammonia, which is prepared via the Haber process from nitrogen. Methanol is prepared from carbon monoxide.

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 olefin metathesis using Grubbs' catalyst, the Heck reaction, and Friedel-Crafts reactions.

Because most bioactive compounds are chiral, many pharmaceuticals are produced by enantioselective catalysis (catalytic asymmetric synthesis).

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.[11] Many other foodstuffs are prepared via biocatalysis (see below).

Biology

In nature, enzymes are catalysts in metabolism and catabolism. Most biocatalysts are protein-based, i.e. enzymes, but other classes of biomolecules also exhibit catalytic properties including ribozymes, and synthetic deoxyribozymes.[12]

Biocatalysts can be thought of as intermediate between homogenous 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, concentration of enzyme, 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.

Enzymes are employed to prepare many commodity chemicals including high-fructose corn syrup and acrylamide.

In the environment

Catalysis impacts 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

In a general sense, anything that increases the rate of a process is a "catalyst", a term derived from Greek καταλύειν, meaning "to annul," or "to untie," or "to pick up." The phrase catalysed processes was coined by Jöns Jakob Berzelius in 1836[13] to describe reactions that are accelerated by substances that remain unchanged after the reaction. Other early chemists involved in catalysis were Alexander Mitscherlich who referred to contact processes and Johann Wolfgang Döbereiner who spoke of contact action and whose lighter based on hydrogen and a platinum sponge became a huge commercial success in the 1820s. Humphry Davy discovered the use of platinum in catalysis. 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.[14]

Inhibitors, poisons and promoters

Substances that reduce the action of catalysts are called catalyst inhibitors if reversible, and catalyst poisons if irreversible. Promoters are substances that increase the catalytic activity, particularly when not being catalysts unto themselves.

The inhibitor may modify selectivity in addition to rate. For instance, in the reduction of ethyne to ethene, the catalyst is palladium (Pd) partly "poisoned" with lead(II) acetate (Pb(CH3COO)2). Without the deactivation of the catalyst, the ethene produced will be further reduced to ethane.[15][16]

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 surface randomly will tend to reduce the number of uncontaminated large planes but leave proportionally more smaller sites free, thus changing the hydrogenation vs. hydrogenolysis selectivity. Many other mechanisms are also possible.

Promoters can cover up surface to prevent 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

  1. ↑ "The 12 Principles of Green Chemistry". United States Environmental Protection Agency. http://www.epa.gov/greenchemistry/pubs/principles.html. Retrieved 2006-07-31. 
  2. ↑ "Genie in a Bottle". University of Minnesota. 2005-03-02. http://www.chem.umn.edu/services/lecturedemo/info/genie.htm. 
  3. ↑ Masel, Richard I. “Chemical Kinetics and Catalysis” Wiley-Interscience, New York, 2001. ISBN 0471241970.
  4. ↑ Chemical & Engineering News, 16 February 2009, "Making Water Step by Step", p. 10
  5. ↑ Robertson, A.J.B. Catalysis of Gas Reactions by Metals. Logos Press, London, 1970.
  6. ↑ Helmut Knözinger, Karl Kochloefl “Heterogeneous Catalysis and Solid Catalysts” in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_313. Article Online Posting Date: January 15, 2003
  7. ↑ Arno Behr “Organometallic Compounds and Homogeneous Catalysis” Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a18_215. Article Online Posting Date: June 15, 2000
  8. ↑ Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 978-3-29390-6
  9. ↑ "Recognizing the Best in Innovation: Breakthrough Catalyst". R&D Magazine, September 2005, pg 20.
  10. ↑ http://www.climatetechnology.gov/library/2005/tech-options/tor2005-143.pdf
  11. ↑ "Types of catalysis". Chemguide. http://www.chemguide.co.uk/physical/catalysis/introduction.html. Retrieved 2008-07-09. 
  12. ↑ Nelson, D. L.; Cox, M. M. "Lehninger, Principles of Biochemistry" 3rd Ed. Worth Publishing: New York, 2000. ISBN 1-57259-153-6.
  13. ↑ K.J. Laidler and J.H. Meiser, Physical Chemistry, Benjamin/Cummings (1982), p.423
  14. ↑ M.W. Roberts (2000). "Birth of the catalytic concept (1800-1900)". Catalysis Letters 67 (1): 1–4. doi:10.1023/A:1016622806065. http://www.springerlink.com/content/qm3732u7x7577224/fulltext.pdf. 
  15. ↑ W.P. Jencks, “Catalysis in Chemistry and Enzymology” McGraw-Hill, New York, 1969. ISBN 0070323054
  16. ↑ Myron L Bender, Makoto Komiyama, Raymond J Bergeron “The Bioorganic Chemistry of Enzymatic Catalysis” Wiley-Interscience, Hoboken, U.S., 1984 ISBN 0471059919

External links

Basic reaction mechanisms
Nucleophilic substitution
Unimolecular nucleophilic substitution (SN1) · Bimolecular nucleophilic substitution (SN2) · Nucleophilic aromatic substitution (SNAr) · Nucleophilic internal substitution (SNi)
Elimination reaction
Unimolecular elimination (E1) · E1cB elimination reaction · Bimolecular elimination (E2)
Related topics
Elementary reaction · Molecularity · Stereochemistry · Catalysis · Collision theory · Solvent effects · Arrow pushing
Chemical kinetics
Rate equation · Rate-determining step