Heterogeneous gold catalysis refers to the use of elemental gold as a heterogeneous catalyst. As in most heterogeneous catalysis, the metal is typically supported on metal oxide. Furthermore, as seen in other heterogeneous catalysts, activity increases with a decreasing diameter of supported gold clusters. Several industrially relevant processes are also observed such as H2 activation, Water-gas shift reaction, and hydrogenation. One or two gold-catalyzed reactions may have been commercialized.
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 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 (α-Fe2O3), cobalt(II/III) oxide (Co3O4) and nickel(II) oxide (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 preliminary commercial applications for the industrial production of vinyl chloride (precursor to polyvinyl chloride or PVC) and methyl methacrylate. 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.
CO oxidation Gold can be a very active catalyst in oxidation of carbon monoxide (CO), i.e. the reaction of CO with molecular oxygen to produce carbon dioxide (CO2). Particles of 2 to 5 nm exhibit high catalytic activities. Supported gold clusters, thin films and nanoparticles are one to two orders of magnitude more active than atomically dispersed gold cations or unsupported metallic gold.
Gold cations can be dispersed atomically on basic metal oxide supports such as MgO 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 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, 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 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 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 on the partial pressures 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. 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 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, an industrial process for the production of dihydrogen (H2), involves the reaction of carbon monoxide - water mixture (syngas) to hydrogen and carbon dioxide. Gold catalysts have been proposed as an alternative for water gas shift at low temperatures, viz. < 523 K (250 °C).
Epoxidations Although the epoxidation of ethylene is highly efficient with Ag catalysts, propylene epoxidation is problematic. Gold on titanium silicate-1 (TS-1) molecular sieve provided > 90% selectivity at ~ 7% propylene 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.
In absence of H2 in the liquid phase. 1% Au/graphite gives ~80% selectivities for cis-cyclooctene to cyclooctene oxide at 7-8% conversion, 353 K (80 °C), and 3 MPa O2 in absence of hydrogen or solvent. 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 activation on gold. While hydrogen dissociates on Pd and Pt without an energy barrier, 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) terraces, nor on (331) 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 in hydrogenation reactions.
One of the early studies (1966) of hydrogenation on supported, highly dispersed gold was performed with 1-butene and cyclohexene in the gas phase at 383 K (110 °C). The reaction rate was found to be first order with respect 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 to 1-butene 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 hydrogenation on Au/SiO2, reaction rates were determined using D2 and H2. Because the reaction with deuterium was substantially slower, it was suggested that the rate-determining step in alkene hydrogenation was the cleavage of the H-H bond. Lastly, ethylene hydrogenation was studied on Au/MgO at atmospheric pressure and 353 K (80 °C) with EXAFS, XANES and IR spectroscopy, suggesting that the active species might be Au+3 and the reaction intermediate, an ethylgold species.
Gold catalysts are especially selective in the hydrogenation of α,β-insaturated aldehydes, i.e. aldehydes containing a C=C double bond on the carbon adjacent to the carbonyl. Gold catalysts are able to hydrogenate only the carbonyl group, so that the aldehyde is transformed to the corresponding alcohol, while leaving the C=C double bond untouched. In the hydrogenation of crotonaldehyde to crotyl alcohol, 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, citral, 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. Because the round morphology provides a higher relative amount of low-coordinated metal surface sites, the higher activity observed with Au/TiO2 compared to Au/ZnO is explained. 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 images that indium thin films 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.