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. Substances that slow a catalyst's effect in a
chemical reaction are called inhibitors (or negative catalysts).
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
slowest 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.
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, as opposed to stoichiometric reactions in which all reactants are consumed and more side products are formed. The most common catalyst is the hydrogen ion (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 creates water and oxygen, as shown below.
- 2 H2O2 → 2 H2O + O2
General principles of catalysis
Typical mechanism
catalytic cycle
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)
- X + Y → Z
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.
Catalysis and reaction energetics
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.
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 productivity of a catalyst can be described by the turn over number (or TON) and the catalytic activity by the turn over frequency (TOF), which is the TON per time unit. The biochemical equivalent is the enzyme unit. For more information on the 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. 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).
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, higher-order oxides, graphitic carbon, nanoparticles, nanodots, and facets of bulk materials. Transition metals are often used to catalyze redox reactions (oxidation, hydrogenation). Examples are nickel, such as Raney nickel for hydrogenation, and vanadium(V) oxide for oxidation of sulfur dioxide into sulfur trioxide. Many catalytic processes, especially those used in organic synthesis, require so called "late transition metals", which include palladium, platinum, gold, ruthenium, rhodium, and iridium.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 (enzymes) are often seen as a separate group.Heterogeneous catalysts
Heterogeneous catalysis
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. Another place where a heterogeneous catalyst is applied is in the contact process (oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid).
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 activated carbon. Specialized supports include silicon dioxide, titanium dioxide, calcium carbonate, and barium sulfate.
Homogeneous catalysts
Homogeneous catalysis
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. For inorganic
chemists, homogeneous catalysis is often synonymous with organometallic
catalysts. Electrocatalysts
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 to water, either to hydroxide or hydrogen
peroxide.Organocatalysis
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 reduce 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 in 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.Significance of catalysis
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
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. Many other foodstuffs are prepared via biocatalysis (see below).Biology
Biocatalysis
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. 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 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.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, even though they are not catalysts by themselves.Inhibitors are sometimes referred to as "negative catalysts" since they decrease the reaction rate. However they do not work by introducing a reaction path with higher activation energy, as this term might suggest; this would not reduce the rate since the reaction would continue to occur by the non-catalyzed path. Instead they act either by inactivating catalysts, or by removing reaction intermediates such as free radicals.
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.
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.
Comments
Post a Comment