Heterogeneous gold catalysis
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Heterogeneous gold catalysis refers to the
catalysis Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
of chemical reactions by
gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile met ...
, typically supported on metal oxide substrates. Despite the well known inertness of bulk gold, decreasing the diameter of supported gold clusters to c. 2 to 5 nm result in high catalytic activities towards low-temperature
carbon monoxide Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simple ...
(CO) oxidation. Several other industrially relevant reactions are also observed such as H2 activation, water gas shift, and
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a Catalysis, catalyst such as nickel, palladium or platinum. The process is commonly employed to redox, reduce or S ...
. The high activity of supported gold clusters has been proposed to arise from a combination of structural changes, quantum-size effects and support effects that preferentially tune the
electronic structure In quantum chemistry, electronic structure is the state of motion of electrons in an electrostatic field created by stationary nuclei. The term encompasses both the wave functions of the electrons and the energies associated with them. Electro ...
of gold such that optimal binding of adsorbates during the catalytic cycle is enabled. The selectivity and activity of gold nanoparticles can be finely tuned by varying the choice of support material, with e.g. titania (TiO2),
hematite Hematite (), also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of . ...
(α-Fe2O3), cobalt(II/III) oxide (Co3O4) and
nickel(II) oxide Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to r ...
(NiO) serving as the most effective support materials for facilitating the catalysis of CO combustion. Besides enabling an optimal dispersion of the nanoclusters, the support materials have been suggested to promote catalysis by altering the size, shape, strain and charge state of the cluster. A precise shape control of the deposited gold clusters has been shown to be important for optimizing the catalytic activity, with hemispherical, few atomic layers thick nanoparticles generally exhibiting the most desirable catalytic properties due to maximized number of high-energy edge and corner sites.


Proposed applications

In the past, heterogeneous gold catalysts have found commercial applications for the industrial production of polyvinyl chloride (PVC),
methyl methacrylate Methyl methacrylate (MMA) is an organic compound with the formula CH2=C(CH3)COOCH3. This colorless liquid, the methyl ester of methacrylic acid (MAA), is a monomer produced on a large scale for the production of poly(methyl methacrylate) (PMMA ...
, and
catalytic converter A catalytic converter is an exhaust emission control device that converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalyzing a redox reaction. Catalytic converters are usually ...
s. Traditionally, PVC production uses mercury catalysts and leads to serious environmental concerns. China accounts for 50% of world's mercury emissions and 60% of China's mercury emission is caused by PVC production. Although gold catalysts are slightly expensive, overall production cost is affected by only ~1%. Therefore, green gold catalysis is considered valuable. The price fluctuation in gold has later led to cease the operations based on their use in catalytic converters. Very recently, there has been a lot of developments in gold catalysis for the synthesis of organic molecules including the C-C bond forming homocoupling or cross-coupling reactions and it has been speculated that some of these catalysts could find applications in various fields.


CO oxidation

Gold can be a very active catalyst in oxidation of
carbon monoxide Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simple ...
(CO), i.e. the reaction of CO with
molecular oxygen There are several known allotropes of oxygen. The most familiar is molecular oxygen (O2), present at significant levels in Earth's atmosphere and also known as dioxygen or triplet oxygen. Another is the highly reactive ozone (O3). Others are: *A ...
to produce
carbon dioxide Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...
(CO2). Supported gold clusters,
thin film A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many ap ...
s and
nanoparticle A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 1 ...
s are one to two orders of magnitude more active than atomically dispersed gold
cations An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
or unsupported
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
lic gold. Gold cations can be dispersed atomically on basic metal oxide supports such as
MgO Magnesium oxide ( Mg O), or magnesia, is a white hygroscopic solid mineral that occurs naturally as periclase and is a source of magnesium (see also oxide). It has an empirical formula of MgO and consists of a lattice of Mg2+ ions and O2− ions ...
and La2O3. Monovalent and trivalent gold cations have been identified, the latter being more active but less stable than the former. The turnover frequency (TOF) of CO oxidation on these cationic gold catalysts is in the order of magnitude of 0.01 s−1, exhibiting the very high
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules pe ...
of 138 kJ/mol. Supported gold nanoclusters with a diameter < 2 nm are active to CO oxidation with turnover number (TOF) in the order of magnitude of 0.1 s−1. It has been observed that clusters with 8 to 100 atoms are catalytically active. The reason is that, on one hand, eight atoms are the minimum necessary to form a stable, discrete energy band structure, and on the other hand, d-band splitting decreases in clusters with more than 100 atoms, resembling the bulk electronic structure. The support has a substantial effect on the electronic structure of gold clusters. Metal hydroxide supports such as Be(OH)2, Mg(OH)2, and La(OH)3, with gold clusters of < 1.5 nm in diameter constitute highly active catalysts for CO oxidation at 200 K (-73 °C). By means of techniques such as HR-TEM and
EXAFS Extended X-ray absorption fine structure (EXAFS), along with X-ray absorption near edge structure (XANES), is a subset of X-ray absorption spectroscopy ( XAS). Like other absorption spectroscopies, XAS techniques follow Beer's law. The X-ray ...
, it has been proven that the activity of these catalysts is due exclusively to clusters with 13 atoms arranged in an icosahedron structure. Furthermore, the metal loading should exceed 10 wt% for the catalysts to be active. Gold nanoparticles in the size range of 2 to 5 nm catalyze CO oxidation with a TOF of about 1 s−1 at temperatures below 273 K (0 °C). The catalytic activity of nanoparticles is brought about in the absence of moisture when the support is
semiconductive A semiconductor is a material which has an electrical conductivity value falling between that of a conductor, such as copper, and an insulator, such as glass. Its resistivity falls as its temperature rises; metals behave in the opposite way. ...
or reducible, e.g. TiO2, MnO2, Fe2O3, ZnO, ZrO2, or CeO2. However, when the support is insulating or non-reducible, e.g. Al2O3 and SiO2, a moisture level > 5000 ppm is required for activity at room temperature. In the case of powder catalysts prepared by wet methods, the surface OH groups on the support provide sufficient aid as co-catalysts, so that no additional moisture is necessary. At temperatures above 333 K (60 °C), no water is needed at all. The apparent
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules pe ...
of CO oxidation on supported gold powder catalysts prepared by wet methods is 2-3 kJ/mol above 333 K (60 °C) and 26-34 kJ/mol below 333 K. These energies are low, compared to the values displayed by other noble metal catalysts (80-120 kJ/mol). The change in activation energy at 333 K can be ascribed to a change in reaction mechanism. This explanation has been supported experimentally. At 400 K (127 °C), the reaction rate per surface Au atom is not dependent on particle diameter, but the reaction rate per perimeter Au atom is directly proportional to particle diameter. This suggests that the mechanism above 333 K takes place on the gold surfaces. By contrast, at 300 K (27 °C), the reaction rate per surface Au atom is inversely proportional to particle diameter, while the rate per perimeter interface does not depend on particle size. Hence, CO oxidation occurs on the perimeter sites at room temperature. Further information on the reaction mechanism has been revealed by studying the dependency of the
reaction rate The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit ...
on the
partial pressure In a mixture of gases, each constituent gas has a partial pressure which is the notional pressure of that constituent gas as if it alone occupied the entire volume of the original mixture at the same temperature. The total pressure of an ideal gas ...
s of the reactive species. Both at 300 K and 400 K, there is a first order rate dependency on CO partial pressure up to 4 Torr (533 Pa), above which the reaction is zero order. With respect to O2, the reaction is zero order above 10 Torr (54.7 kPa) at both 300 and 400 K. The order with respect to O2 at lower partial pressures is 1 at 300 K and 0.5 at 400 K. The shift towards zero order indicates that the catalyst's active sites are saturated with the species in question. Hence, a Langmuir-Hinshelwood mechanism has been proposed, in which CO adsorbed on gold surfaces reacts with O adsorbed at the edge sites of the gold nanoparticles. The need to use oxide supports, and more specifically reducible supports, is due to their ability to activate
dioxygen There are several known allotropes of oxygen. The most familiar is molecular oxygen (O2), present at significant levels in Earth's atmosphere and also known as dioxygen or triplet oxygen. Another is the highly reactive ozone (O3). Others are: *A ...
. Gold nanoparticles supported on inert materials such as carbon or polymers have been proven inactive in CO oxidation. The aforementioned dependency of some catalysts on water or moisture also relates to oxygen activation. The ability of certain reducible oxides, such as MnO2, Co3O4, and
NiO are two wrathful and muscular guardians of the Buddha standing today at the entrance of many Buddhist temples in East Asian Buddhism in the form of frightening wrestler-like statues. They are dharmapala manifestations of the bodhisattva Vajra ...
to activate oxygen in dry conditions (< 0.1 ppm H2O) can be ascribed to the formation of oxygen defects during pretreatment.


Water gas shift

Water gas shift is the most widespread industrial process for the production of
dihydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, and ...
, H2. It involves the reaction of carbon monoxide and water (
syngas Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide, in various ratios. The gas often contains some carbon dioxide and methane. It is principly used for producing ammonia or methanol. Syngas is combustible and can be used as ...
) to form hydrogen and carbon dioxide as a byproduct. In many catalytic reaction schemes, one of the
elementary reaction An elementary reaction is a chemical reaction in which one or more chemical species react directly to form products in a single reaction step and with a single transition state. In practice, a reaction is assumed to be elementary if no reaction in ...
s is the oxidation of CO with an
adsorbed Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a ...
oxygen species. Gold catalysts have been proposed as an alternative for water gas shift at low temperatures, viz. < 523 K (250 °C). This technology is essential to the development of
solid oxide fuel cell A solid oxide fuel cell (or SOFC) is an electrochemical conversion device that produces electricity directly from oxidizing a fuel. Fuel cells are characterized by their electrolyte material; the SOFC has a solid oxide or ceramic electrolyte. A ...
s. Hematite has been found to be an appropriate catalyst support for this purpose. Furthermore, a bimetallic Au- Ru/Fe2O3 catalyst has been proven highly active and stable for low-temperature water gas shift. Titania and
ceria Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial produ ...
have also been used as supports for effective catalysts. Unfortunately, Au/ CeO2 is prone to deactivation caused by surface-bound
carbonate A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate g ...
or
formate Formate (IUPAC name: methanoate) is the conjugate base of formic acid. Formate is an anion () or its derivatives such as ester of formic acid. The salts and esters are generally colorless.Werner Reutemann and Heinz Kieczka "Formic Acid" in ''Ull ...
species. Although gold catalysts are active at room temperature to CO oxidation, the high amounts of water involved in water gas shift require higher temperatures. At such temperatures, gold is fully reduced to its metallic form. However, the activity of e.g. Au/CeO2 has been enhanced by CN treatment, whereby metallic gold is leached, leaving behind highly active cations. According to DFT calculations, the presence of such Au cations on the catalyst is allowed by empty, localized nonbonding f states in CeO2. On the other hand,
STEM Stem or STEM may refer to: Plant structures * Plant stem, a plant's aboveground axis, made of vascular tissue, off which leaves and flowers hang * Stipe (botany), a stalk to support some other structure * Stipe (mycology), the stem of a mushro ...
studies of Au/CeO2 have revealed nanoparticles of 3 nm in diameter. Water gas shift has been proposed to occur ar the interface of Au nanoparticles and the reduced CeO2 support.


Epoxidations

Although the epoxidation of
ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene i ...
is routinely achieved in the industry with selectivities as high as 90% on Ag catalysts, most catalysts provided < 10%
selectivity Selectivity may refer to: Psychology and behaviour * Choice, making a selection among options * Discrimination, the ability to recognize differences * Socioemotional selectivity theory, in social psychology Engineering * Selectivity (radio), a ...
for propylene epoxidation. Using a gold catalyst supported on titanium silicate-1 (TS-1)
molecular sieve A molecular sieve is a material with pores (very small holes) of uniform size. These pore diameters are similar in size to small molecules, and thus large molecules cannot enter or be adsorbed, while smaller molecules can. As a mixture of molecu ...
, yields of 350 g/h per gram of gold were obtained at 473 K (200 °C). The reaction took place in the gas phase. Furthermore, using
mesoporous A mesoporous material (or super nanoporous ) is a nanoporous material containing pores with diameters between 2 and 50 nm, according to IUPAC nomenclature. For comparison, IUPAC defines microporous material as a material having pores smaller ...
titanosilicate supports (Ti- MCM-41 and Ti- MCM-48), gold catalysts provided > 90% selectivity at ~ 7% propylene
conversion Conversion or convert may refer to: Arts, entertainment, and media * "Conversion" (''Doctor Who'' audio), an episode of the audio drama ''Cyberman'' * "Conversion" (''Stargate Atlantis''), an episode of the television series * "The Conversion" ...
, 40% H2 efficiency, and 433 K (160 °C). The active species in these catalysts were identified to be hemispherical gold nano-crystals of less than 2 nm in diameter in intimate contact with the support. Alkene epoxidation has been demonstrated in absence of H2 reductant in the liquid phase. For example, using 1% Au/
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large ...
, ~80% selectivities of
cis-cyclooctene ''cis''-Cyclooctene is a cycloalkene with the formula (CH2)6(CH)2. It is a colorless liquid that is used industrially to produce a polymer. It is also a ligand in organometallic chemistry. Cyclooctene is the smallest cycloalkene that can be iso ...
to cyclooctene oxide (analogous to
cyclohexene oxide Cyclohexene oxide is a Epoxy#Aliphatic, cycloaliphatic epoxide. It can react in cationic polymerization to poly(cyclohexene oxide). As cyclohexene is monovalent ion, monovalent, poly(cyclohexene oxide) is a thermoplastic. Production Cyclohexene ...
) were obtained at 7-8% conversion, 353 K (80 °C), and 3 MPa O2 in absence of hydrogen or solvent. Other liquid-phase selective oxidations have been achieved with saturated hydrocarbons. For instance,
cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colorless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...
has been converted to
cyclohexanone Cyclohexanone is the organic compound with the formula (CH2)5CO. The molecule consists of six-carbon cyclic molecule with a ketone functional group. This colorless oily liquid has an odor reminiscent of acetone. Over time, samples of cyclohexan ...
and
cyclohexanol Cyclohexanol is the organic compound with the formula HOCH(CH2)5. The molecule is related to cyclohexane by replacement of one hydrogen atom by a hydroxyl group. This compound exists as a deliquescent colorless solid with a camphor-like odor, w ...
with a combined selectivity of ~100% on gold catalysts. Product selectivities can be tuned in liquid phase reactions by the presence or absence of solvent and by the nature of the latter, viz. water,
polar Polar may refer to: Geography Polar may refer to: * Geographical pole, either of two fixed points on the surface of a rotating body or planet, at 90 degrees from the equator, based on the axis around which a body rotates * Polar climate, the c ...
, or
nonpolar In chemistry, polarity is a separation of electric charge leading to a molecule or its chemical groups having an electric dipole moment, with a negatively charged end and a positively charged end. Polar molecules must contain one or more polar ...
. With gold catalysts, the catalyst's support has less influence on reactions in the liquid phase than on reactions in the gas phase.


Selective hydrogenations

Typical hydrogenation catalysts are based on metals from the 8, 9, and 10 groups, such as Ni, Ru, Pd, and Pt. By comparison, gold has a poor catalytic activity for hydrogenation. This low activity is caused by the difficulty of
dihydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, and ...
activation on gold. While hydrogen dissociates on Pd and Pt without an
energy barrier In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules pe ...
, dissociation on Au( 111) has an energy barrier of ~1.3 eV, according to DFT calculations. These calculations agree with experimental studies, in which hydrogen dissociation was not observed on gold ( 111) or (
110 110 may refer to: *110 (number), natural number *AD 110, a year *110 BC, a year *110 film, a cartridge-based film format used in still photography *110 (MBTA bus), Massachusetts Bay Transportation Authority bus route *110 (song), 2019 song by Capi ...
) terraces, nor on (
331 __NOTOC__ Year 331 (Roman numerals, CCCXXXI) was a common year starting on Friday (link will display the full calendar) of the Julian calendar. At the time, it was known as the Year of the Consulship of Bassus and Ablabius (or, less frequent ...
) steps. No dissociation was observed on these surfaces either at room temperature or at 473 K (200 °C). However, the rate of hydrogen activation increases for Au nanoparticles. Notwithstanding its poor activity, nano-sized gold immobilized in various supports has been found to provide a good
selectivity Selectivity may refer to: Psychology and behaviour * Choice, making a selection among options * Discrimination, the ability to recognize differences * Socioemotional selectivity theory, in social psychology Engineering * Selectivity (radio), a ...
in hydrogenation reactions. One of the early studies (1966) of hydrogenation on supported, highly dispersed gold was performed with
1-butene 1-Butene (or 1-Butylene) is the organic compound with the formula CH3CH2CH=CH2. It is a colorless gas that is easily condensed to give a colorless liquid. It is classified as a linear alpha-olefin. It is one of the isomers of butene (butylene). I ...
and
cyclohexene Cyclohexene is a hydrocarbon with the formula C6H10. This cycloalkene is a colorless liquid with a sharp smell. It is an intermediate in various industrial processes. Cyclohexene is not very stable upon long term storage with exposure to light a ...
in the gas phase at 383 K (110 °C). The
reaction rate The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit ...
was found to be first order with trespect to alkene pressure and second order with respect to chemisorbed hydrogen. In later works, it was shown that gold-catalyzed hydrogenation can be highly sensitive to Au loading (hence to particle size) and to the nature of the support. For example, 1-pentene hydrogenation occurred optimally on 0.04 wt% Au/ SiO2, but not at all on Au/ γ-Al2O3. By contrast, the hydrogenation of
1,3-butadiene 1,3-Butadiene () is the organic compound with the formula (CH2=CH)2. It is a colorless gas that is easily condensed to a liquid. It is important industrially as a precursor to synthetic rubber. The molecule can be viewed as the union of two viny ...
to
1-butene 1-Butene (or 1-Butylene) is the organic compound with the formula CH3CH2CH=CH2. It is a colorless gas that is easily condensed to give a colorless liquid. It is classified as a linear alpha-olefin. It is one of the isomers of butene (butylene). I ...
was shown to be relatively insensitive to Au particle size in a study with a series of Au/Al2O3 catalysts prepared by different methods. With all the tested catalysts, conversion was ~100% and selectivity, < 60%. Concerning reaction mechanisms, in a study of
propylene Propylene, also known as propene, is an unsaturated organic compound with the chemical formula CH3CH=CH2. It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petrole ...
hydrogenation on Au/SiO2,
reaction rate The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit ...
s were determined using D2 and H2. Because the reaction with
deuterium Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two Stable isotope ratio, stable isotopes of hydrogen (the other being Hydrogen atom, protium, or hydrogen-1). The atomic nucleus, nucleus of a deuterium ato ...
was substantially slower, it was suggested that the
rate-determining step In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS or RD-step or r/d step) or rate-limiting step. For a given reaction mechanism, the prediction of the ...
in alkene hydrogenation was the cleavage of the H-H bond. Lastly,
ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene i ...
hydrogenation was studied on Au/
MgO Magnesium oxide ( Mg O), or magnesia, is a white hygroscopic solid mineral that occurs naturally as periclase and is a source of magnesium (see also oxide). It has an empirical formula of MgO and consists of a lattice of Mg2+ ions and O2− ions ...
at atmospheric pressure and 353 K (80 °C) with
EXAFS Extended X-ray absorption fine structure (EXAFS), along with X-ray absorption near edge structure (XANES), is a subset of X-ray absorption spectroscopy ( XAS). Like other absorption spectroscopies, XAS techniques follow Beer's law. The X-ray ...
,
XANES X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra ( XAS) of condensed matter due to the ...
and
IR spectroscopy Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functiona ...
, suggesting that the active species might be Au+3 and the
reaction intermediate In chemistry, a reaction intermediate or an intermediate is a molecular entity that is formed from the reactants (or preceding intermediates) but is consumed in further reactions in stepwise chemical reactions that contain multiple elementary st ...
, an ethylgold species. Gold catalysts are especially selective in the hydrogenation of α,β-insaturated aldehydes, i.e.
aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl grou ...
s containing a C=C
double bond In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist betw ...
on the carbon adjacent to the
carbonyl In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups. A compound containing a ...
. Gold catalysts are able to hydrogenate only the carbonyl group, so that the aldehyde is transformed to the corresponding
alcohol Alcohol most commonly refers to: * Alcohol (chemistry), an organic compound in which a hydroxyl group is bound to a carbon atom * Alcohol (drug), an intoxicant found in alcoholic drinks Alcohol may also refer to: Chemicals * Ethanol, one of sev ...
, while leaving the C=C double bond untouched. In the hydrogenation of
crotonaldehyde Crotonaldehyde is a chemical compound with the formula CH3CH=CHCHO. The compound is usually sold as a mixture of the ''E''- and ''Z''-isomers, which differ with respect to the relative position of the methyl and formyl groups. The ''E''-isomer ...
to
crotyl alcohol Crotyl alcohol, or crotonyl alcohol, is an unsaturated alcohol. It is a colourless liquid that is moderately soluble in water and miscible with most organic solvents. Two isomers of this alcohol exist, cis and trans. It can be synthesized by th ...
, 80% selectivity was attained at 5-10% conversion and 523 K (250 °C) on Au/ ZrO2 and Au/ ZnO. The selectivity increased along with Au particle size in the range of ~2 to ~5 nm. Other instances of this reaction include
acrolein Acrolein (systematic name: propenal) is the simplest unsaturated aldehyde. It is a colorless liquid with a piercing, acrid smell. The smell of burnt fat (as when cooking oil is heated to its smoke point) is caused by glycerol in the burning fa ...
,
citral Citral is an acyclic monoterpene aldehyde, and being a monoterpene, it is made of two isoprene units. Citral is a collective term which covers two geometric isomers that have their own separate names; the ''E''-isomer is named geranial (''trans ...
, benzal acetone, and pent-3-en-2-one. The activity and selectivity of gold catalysts for this reaction has been linked to the morphology of the nanoparticles, which in turn is influenced by the support. For example, round particles tend to form on TiO2, while ZnO promotes particles with clear facets, as observed by
TEM Tem or TEM may refer to: Acronyms * Threat and error management, an aviation safety management model. * Telecom Expense Management * Telecom Equipment Manufacturer * TEM (currency), local to Volos, Greece * TEM (nuclear propulsion), a Russian ...
. Because the round morphology provides a higher relative amount of low- coordinated metal surface sites, the higher activity observerd with Au/TiO2 compared to Au/ZnO is explained. Finally, a bimetallic Au- In/ZnO catalyst has been observed to improve the selectivity towards the hydrogenation of the carbonyl in acrolein. It was observed in
HRTEM High-resolution transmission electron microscopy is an imaging mode of specialized transmission electron microscopes that allows for direct imaging of the atomic structure of samples. It is a powerful tool to study properties of materials on the a ...
images that
indium Indium is a chemical element with the symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts p ...
thin film A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many ap ...
s decorate some of the facets of the gold nanoparticle. The promoting effect on selectivity might result from the fact that only the Au sites that promote side-reactions are decorated by In. A strategy that in many reactions has succeeded at improving gold's catalytic activity without impairing its selectivity is to synthesize bimetallic Pd-Au or Pt-Au catalysts. For the hydrogenation of
1,3-butadiene 1,3-Butadiene () is the organic compound with the formula (CH2=CH)2. It is a colorless gas that is easily condensed to a liquid. It is important industrially as a precursor to synthetic rubber. The molecule can be viewed as the union of two viny ...
to
butene Butene, also known as butylene, is an alkene with the formula . The word ''butene'' may refer to any of the individual compounds. They are colourless gases that are present in crude oil as a minor constituent in quantities that are too small for ...
s, model surfaces of Au( 111), Pd-Au( 111), Pd-Au(
110 110 may refer to: *110 (number), natural number *AD 110, a year *110 BC, a year *110 film, a cartridge-based film format used in still photography *110 (MBTA bus), Massachusetts Bay Transportation Authority bus route *110 (song), 2019 song by Capi ...
), and Pd( 111) were studied with
LEED Leadership in Energy and Environmental Design (LEED) is a green building certification program used worldwide. Developed by the non-profit U.S. Green Building Council (USGBC), it includes a set of rating systems for the design, construction ...
, AES, and LEIS. A selectivity of ~100% was achieved on Pd70Au30( 111) and it was suggested that Au might promote the desorption of the product during the reaction. A second instance is the hydrogenation of ''p''-chloronitrobenzene to ''p''-chloroaniline, in which selectivity suffers with typical hydrogenation catalysts due to the
parallel Parallel is a geometric term of location which may refer to: Computing * Parallel algorithm * Parallel computing * Parallel metaheuristic * Parallel (software), a UNIX utility for running programs in parallel * Parallel Sysplex, a cluster of IBM ...
hydrodechlorination to
aniline Aniline is an organic compound with the formula C6 H5 NH2. Consisting of a phenyl group attached to an amino group, aniline is the simplest aromatic amine In organic chemistry, an aromatic amine is an organic compound consisting of an aroma ...
. However, Pd-Au/Al2O3 (Au/Pd ≥20) has been proven thrice as active as the pure Au catalyst, while being ~100% selective to ''p''-chloroaniline. In a mechanistic study of hydrogenation of nitrobenzenes with Pt-Au/TiO2, the dissociation of H2 was identified as rate-controlling, hence the incorporation of Pt, an efficient hydrogenation metal, highly improved catalytic activity. Dihydrogen dissociated on Pt and the nitroaromatic compound was activated on the Au-TiO2 interface. Finally, hydrogenation was enabled by the spillover of activated H surface species from Pt to the Au surface.


Theoretical background

Bulk metallic gold is known to be inert, exhibiting a surface reactivity at room temperature only towards a few substances such as
formic acid Formic acid (), systematically named methanoic acid, is the simplest carboxylic acid, and has the chemical formula HCOOH and structure . It is an important intermediate in chemical synthesis and occurs naturally, most notably in some ants. Es ...
and sulphur-containing compounds, e.g. H2S and
thiol In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...
s. Within heterogeneous catalysis, reactants
adsorb Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a fl ...
onto the surface of the catalyst thus forming activated intermediates. However, if the adsorption is weak such as in the case of bulk gold, a sufficient perturbation of the reactant electronic structure does not occur and catalysis is hindered ( Sabatier's principle). When gold is deposited as nanosized clusters of less than 5 nm onto metal oxide supports, a markedly increased interaction with adsorbates is observed, thereby resulting in surprising catalytic activities. Evidently, nano-scaling and dispersing gold on metal oxide substrates makes gold less noble by tuning its electronic structure, but the precise mechanisms underlying this phenomenon are as of yet uncertain and hence widely studied. It is generally known that decreasing the size of metallic particles in some dimension to the nanometer scale will yield clusters with a significantly more discrete
electronic band structure In solid-state physics, the electronic band structure (or simply band structure) of a solid describes the range of energy levels that electrons may have within it, as well as the ranges of energy that they may not have (called ''band gaps'' or '' ...
in comparison with the bulk material. This is an example of a quantum-size effect and has been previously correlated with an increased reactivity enabling nanoparticles to bind gas phase molecules more strongly. In the case of TiO2-supported gold nanoparticles, Valden ''et al.'' observed the opening of a
band gap In solid-state physics, a band gap, also called an energy gap, is an energy range in a solid where no electronic states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference (in ...
of approximately 0.2-0.6 eV in the gold electronic structure as the thickness of the deposited particles was decreased below three atomic layers. The two-layer thick supported gold clusters were also shown to be exceptionally active for CO combustion, based on which it was concluded that quantum-size effects inducing a metal-insulator transition play a key role in enhancing the catalytic properties of gold. However, decreasing the size further to a single atomic layer and a diameter of less than 3 nm was reported to again decrease the activity. This has later been explained by a destabilization of clusters composed of very few atoms, resulting in too strong bonding of adsorbates and thus poisoning of the catalyst. The properties of the metal d-band are central for describing the origin of catalytic activity based on electronic effects. According to the d-band model of heterogeneous catalysis, substrate-adsorbate bonds are formed as the discrete energy levels of the adsorbate molecule interacts with the metal d-band, thus forming bonding and antibonding orbitals. The strength of the formed bond depends on the position of the d-band center such that a d-band closer to the
Fermi level The Fermi level of a solid-state body is the thermodynamic work required to add one electron to the body. It is a thermodynamic quantity usually denoted by ''µ'' or ''E''F for brevity. The Fermi level does not include the work required to remove ...
(E_\mathrm) will result in stronger interaction. The d-band center of bulk gold is located far below E_\mathrm, which qualitatively explains the observed weak binding of adsorbates as both the bonding and antibonding orbitals formed upon adsorption will be occupied, resulting in no net bonding. However, as the size of gold clusters is decreased below 5 nm, it has been shown that the d-band center of gold shifts to energies closer to the Fermi level, such that the as formed antibonding orbital will be pushed to an energy above E_\mathrm, hence reducing its filling. In addition to a shift in the d-band center of gold clusters, the size-dependency of the d-band width as well as the 5d_\textd_ spin-orbit splitting has been studied from the viewpoint of catalytic activity. As the size of the gold clusters is decreased below 150 atoms (diameter ca. 2.5 nm), rapid drops in both values occur. This can be attributed to d-band narrowing due to the decreased number of hybridizing valence states of small clusters as well as to the increased ratio of high-energy edge atoms with low coordination to the total number of Au atoms. The effect of the decreased 5d_\textd_ spin-orbit splitting as well as the narrower distribution of d-band states on the catalytic properties of gold clusters cannot be understood via simple qualitative arguments as in the case of the d-band center model. Nevertheless, the observed trends provide further evidence that a significant perturbation of the Au electronic structure occurs upon nanoscaling, which is likely to play a key role in the enhancement of the catalytic properties of gold nanoparticles. A central structural argument explaining the high activity of metal oxide supported gold clusters is based on the concept of periphery sites formed at the junction between the gold cluster and the substrate. In the case of CO oxidation, it has been hypothesized that CO adsorbs onto the edges and corners of the gold clusters, while the activation of oxygen occurs at the peripheral sites. The high activity of edge and corner sites towards adsorption can be understood by considering the high coordinative unsaturation of these atoms in comparison with terrace atoms. The low degree of coordination increases the
surface energy In surface science, surface free energy (also interfacial free energy or surface energy) quantifies the disruption of intermolecular bonds that occurs when a surface is created. In solid-state physics, surfaces must be intrinsically less energe ...
of corner and edge sites, hence making them more active towards binding adsorbates. This is further coupled with the local shift of the d-band center of the unsaturated Au atoms towards energies closer to the Fermi level, which in accordance with the d-band model results in increased substrate-adsorbate interaction and lowering of the adsorption-dissociation energy barriers. Lopez ''et al.'' calculated the adsorption energy of CO and O2 on the Au( 111) terrace on which the Au-atoms have a coordination number of 9 as well as on an Au10 cluster where the most reactive sites have a coordination of 4. They observed that the bond strengths are in general increased by as much as 1 eV, indicating a significant activation towards CO oxidation if one assumes that the activation barriers of surface reactions scale linearly with the adsorption energies ( Brønsted-Evans-Polanyi principle). The observation that hemispherical two-layer gold clusters with a diameter of a few nanometers are most active for CO oxidation is well in line with the assumption that edge and corner atoms serve as the active sites, since for clusters of this shape and size the ratio of edge atoms to the total number of atoms is indeed maximized. The preferential activation of O2 at the perimeter sites is an example of a support effect that promotes the catalytic activity of gold nanoparticles. Besides enabling a proper dispersion of the deposited particles and hence a high surface-to-volume ratio, the metal oxide support also directly perturbs the electronic structure of the deposited gold clusters via various mechanisms, including strain-inducing and charge transfer. For gold deposited on magnesia (MgO), a charge transfer from singly charged oxygen vacancies (F-centers) at the MgO surface to the Au cluster has been observed. This charge transfer induces a local perturbation in the electronic structure of the gold clusters at the perimeter sites, enabling the formation of resonance states as the antibonding 2\pi^*orbital of oxygen interacts with the metal d-band. As the antibonding orbital is occupied, the O-O bond is significantly weakened and stretched, i.e. activated. The activation of O2 at the perimeter sites is also observed for defect-free surfaces and neutral gold clusters, but to a significantly smaller extent. The activity enhancing effect of charge transfer from the substrate to gold has also been reported by Chen and Goodman in the case of a gold bilayer supported on ultrathin TiO2 on Mo(
112 112 may refer to: *112 (number), the natural number following 111 and preceding 113 *112 (band), an American R&B quartet from Atlanta, Georgia **112 (album), ''112'' (album), album from the band of the same name *112 (emergency telephone number), t ...
). In addition to charge transfer between the substrate and the gold nanoparticles, the support material has been observed to increase the catalytic activity of gold by inducing strain as a consequence of lattice mismatch. The induced strains especially affect the Au atoms close to the substrate-cluster interface, resulting in a shift of the local d-band center towards energies closer to the Fermi level. This corroborates the periphery hypothesis and the creation of catalytically active bifunctional sites at the cluster-support interface. Furthermore, the support-cluster interaction directly influences the size and shape of the deposited gold nanoparticles. In the case of weak interaction, less active 3D clusters are formed, whereas if the interaction is stronger more active 2D few-layer structures are formed. This illustrates the ability to fine-tune the catalytic activity of gold clusters via varying the support material as well as the underlying metal upon which the substrate has been grown. Finally, it has been observed that the catalytic activity of supported gold clusters towards CO oxidation is further enhanced by the presence of water. Invoking the periphery hypothesis, water promotes the activation of O2 by co-adsorption onto the perimeter sites where it reacts with O2 to form adsorbed
hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...
(OH*) and hydroperoxo (OOH*) species. The reaction of these intermediates with adsorbed CO is very rapid, and results in the efficient formation of CO2 with concomitant recovery of the water molecule.


See also

*
Gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile met ...
* Gold cluster *
Organogold chemistry Organogold chemistry is the study of compounds containing gold–carbon bonds. They are studied in academic research, but have not received widespread use otherwise. The dominant oxidation states for organogold compounds are I with coordination num ...
*
Colloidal gold Colloidal gold is a sol or colloidal suspension of nanoparticles of gold in a fluid, usually water. The colloid is usually either wine-red coloured (for spherical particles less than 100  nm) or blue/purple (for larger spherical particl ...
*
Heterogeneous catalysis In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Ph ...
*
Cluster chemistry In chemistry, an atom cluster (or simply cluster) is an ensemble of bound atoms or molecules that is intermediate in size between a simple molecule and a nanoparticle; that is, up to a few nanometers (nm) in diameter. The term ''microcluster'' ...
*
Hydrogen spillover In heterogeneous catalysis, hydrogen molecules can be adsorbed and dissociated by the metal catalyst. Hydrogen spillover is the migration of hydrogen atoms from the metal catalyst onto the nonmetal support or adsorbate.Gardes, G. E. E., Pajonk, G. ...
{{colend


References

Gold Chemical reactions Chemical kinetics Catalysis Surface science