Recent Advances in Understanding CO Oxidation on Gold Nanoparticles Using Density Functional Theory

Since the discovery of a series of Au-based catalysts by Haruta et al. considerable progress has been made in understanding the active role of Au in CO oxidation catalysis. This review provides a summary of recent theoretical work performed in this field; in particular it addresses DFT studies of CO oxidation catalysis over free and supported gold nanoparticles. Several properties of the Au particles have been found to contribute to their unique catalytic activity. Of these properties, the low-coordination state of the Au atoms is arguably the most pertinent, although other properties of the Au cluster atoms, such as electronic charge, cannot be ignored. The current consensuses regarding the mechanism for CO oxidation over Au-based catalysts is also discussed. Finally, water-enhanced catalysis of CO oxidation on Au clusters is summarized.     

Reaction of Au(111) with Sulfur and Oxygen: Scanning Tunneling Microscopic Study

The reaction of sulfur and oxygen with the gold surface is important in many technological applications, including heterogeneous catalysis, corrosion, and chemical sensors. We have studied reactions on Au(111) using scanning tunneling microscopy (STM) in order to better understand the surface structure and the origin of gold’s catalytic activity. We find that the Au(111) surface dynamically restructures during deposition of sulfur and oxygen and that these changes in structure promote the reactivity of Au with respect to SO₂ and O₂ dissociation. Specifically, the Au(111) herringbone reconstruction lifts when either S or O is deposited on the surface. We attribute this structural change to the reduction of tensile surface stress via charge redistribution by these electronegative adsorbates. This lifting of the reconstruction was accompanied by the release of gold atoms from the herringbone structure. At high coverage, clusters of gold sulfides or gold oxides form by abstraction of gold atoms from regular terrace sites of the surface. Concomitant with the restructuring is the release of gold atoms from the herringbone structure to produce a higher density of low-coordinated Au sites by forming serrated step edges or small gold islands. These undercoordinated Au atoms may play an essential role in the enhancement of catalytic activity of gold in reactions such as oxygen dissociation or SO₂ decomposition. Our results further elucidate the interaction between sulfur and oxygen and the Au(111) surface and indicate that the reactivity of Au nanoclusters on reducible metal oxides is probably related to the facile release of Au from the edges of these small islands. Our results provide insight into the sintering mechanism which leads to deactivation of Au nanoclusters and into the fundamental limitation in the edge definition in soft lithography using thiol-based self-assembled monolayers (SAMs) on Au. Furthermore, the enhanced reactivity of Au after release of undercoordinated atoms from the surface indicate a relatively insignificant role of an oxide support for high reactivity.     

Investigation of CO Oxidation Transient Kinetics on an Oxygen Pre-covered Au(211) Stepped Surface

The desire to explain the origin(s) of the unexpected catalytic activity of oxide-supported Au nanoparticles for CO oxidation discovered by Haruta and coworkers has stimulated numerous experimental and theoretical studies of Au nanoclusters in the gas phase and on metal oxide supports, and on Au single-crystal surfaces. In order to explore further the reactivity of low-coordination Au step sites, we have performed transient kinetics studies of CO oxidation on an O-precovered, stepped Au(211) single crystal surface. We found behavior similar to that observed previously on flat Au(111) and (110) surfaces; i.e., there is no evidence in these transient kinetics for any special reactivity associated with this stepped Au surface. The CO oxidation reaction rate was highly dependent on the initial oxygen coverage, and we determined an apparent activation energy for CO oxidation of ?7.0 kJ mol^?1 for θ _O ^init  = 0.9 ML. Within the Langmuir-Hinschelwood (LH) reaction scheme, we estimate an activation energy of E _LH = 20–43 kJ mol^?1 on this surface for CO oxidation via this pathway. This is somewhat below the value of 67 kJ mol^?1 predicted by recent theoretical calculations.     

Insights from Theory on the Relationship Between Surface Reactivity and Gold Atom Release

Density functional theory, informed by experimental studies, is used to investigate the interplay of surface morphology, the adsorption site of reactants, the nature of the interaction between adsorbates and the surface, the potential energy landscape for adsorbates on the surface, adsorbate coverage, temperature, and the dynamic evolution of these factors during adsorption and reaction. We summarize our current understanding of Au atom release on the (111) surface and the corresponding effects on adsorption and reactivity. Gold was selected for these investigations because of the recent intense interest in the activity of gold nanoparticles for several important catalytic reactions. Fundamental experimental studies on Au single-crystal surfaces have established that atomic O is extremely active for oxidation of CO and olefins, that the local bonding of O is an important factor in determining the reactivity and selectivity for oxidation, and that Au atom release is induced by electronegative adsorbates, such as O, Cl, and S. These experimental results guided our theoretical studies. Density functional theory is an extremely useful tool since it evaluates the energetics associated with the incorporation of gold into the adsorbate layer, while providing fundamental physical insight into the underlying cause of gold incorporation. We use our results from static DFT calculations along with ab initio molecular dynamics simulations to understand the effect of surface morphology on the activity of gold for CO oxidation. Our investigation of Au atom release and incorporation induced by electronegative atoms clearly illustrates the importance of using experiments in combination with theory to establish the importance of and the underlying reasons for metal atom release and the affect on bonding and reactivity.     

Mechanistic Insights in the Catalytic Synthesis of Vinyl Acetate on Palladium and Gold/Palladium Alloy Surfaces

The reaction pathways for the synthesis of vinyl acetate monomer (VAM) are explored on model palladium and gold–palladium alloy single crystal catalysts by combining experiments carried out in ultrahigh vacuum together with density functional theory calculations and Monte Carlo simulations. Previous work by Goodman has shown that both pure palladium and gold–palladium alloys catalyze VAM formation at high pressures, thereby paving the way for fundamental studies of the pathways for this reaction. The coverages of the reactants and products on the surface were found to play an important role in controlling both the reaction pathways and the selectivity. The high coverages on the catalyst under reaction conditions favor bond-forming reactions while inhibiting bond-breaking reactions. On Pd(111), the reaction is initiated by the coupling of ethylene and surface acetate species to form an acetoxyethyl-palladium intermediate, a bond-forming reaction. The high coverages also act to control the selectivity since VAM is stabilized on the crowded surface. The gold in model Au/Pd(111) and Au/Pd(100) alloys gold preferentially segregates to the surface. In the case of Au/Pd(111) alloys, there is a slightly repulsive interaction between the gold and palladium atoms, resulting in a larger proportion of isolated palladium sites than would be expected if they were randomly distributed, while the longer-range interactions on Au/Pd(100) lead to the formation of ordered surface structures and the existence of isolated palladium sites for gold coverages greater than 0.5 ML. Higher coverages of Au on the Au/Pd(111) and Au/Pd(100) alloys decrease the population of bridging Pd sites and thus increase Pd site isolation. This eliminates the larger Pd ensembles that that lead to the decomposition of VAM and ethylene thus increasing the reaction selectivity and weakens the adsorption of ethylene and acetate which enhances the rate of reaction. Higher coverages of Au, however, also suppress the activation of O₂ which decrease the rate of acid deprotonation thus resulting in optimal Au/Pd compositions.     

Gold supported on well-ordered ceria films: nucleation, growth and morphology in CO oxidation reaction

Structure of gold nanoparticles formed by physical vapor deposition onto thin ceria films was studied by scanning tunneling microscopy (STM). Gold preferentially nucleates on point defects present on the terraces of the well-ordered, fully oxidized films to a low density. The nucleation expands to the terrace step edges, providing a large variety of low-coordinated sites. Only at high coverage, the Au particles grow homogeneously on the oxygen-terminated CeO₂(111) terraces. The morphology of Au particles was further examined by STM in situ and ex situ at elevated (up to 20 mbar) pressures of O₂, CO, and CO + O₂ at 300 K. The particles are found to be stable in O₂ ambient up to 10 mbar, meanwhile gold sintering emerges at CO pressures above ∼1 mbar. Sintering of the Au particles, which mainly proceeds along the step edges of the CeO₂(111) support, is observed in CO + O₂ (1:1) mixture at much lower pressure (∼10⁻³ mbar), thus indicating that the structural stability of the Au/ceria catalysts is intimately connected with its reactivity in the CO oxidation reaction.     

Gold Supported on Oxide Surfaces: Environmental Effects as Studied by STM

This paper begins by providing a short review of STM studies of gold particles supported on oxide surfaces. Following this, the morphology of Au particles deposited on thin FeO(111) films at elevated pressures of CO, O₂, CO+O₂, and H₂ has been examined using in situ STM at room temperature. The Au particles are found to be quite stable in oxygen and hydrogen environments at pressures up to 2 mbar. However, in CO and CO+O₂ atmospheres, the destabilization of Au particles located at the step edges occurs leading to the formation of mobile Au species, which migrate across the oxide surface. General problems encountered with high-pressure STM studies are discussed, and data clearly showing the effects of ambient gas impurities is provided. These effects may lead to erroneous conclusions, particularly about morphological changes of and CO dissociation on the gold surfaces at elevated pressures.     

Graphene growth on Pt(111) and Au(111) using a MBE carbon solid-source

In this work we present a Molecular Beam Epitaxy (MBE) growth method to obtain graphene on noble metals using evaporation of carbon atoms from a carbon solid-source in ultra-high vacuum conditions. We have synthesized graphene (G) on different metal surfaces: from a well studied substrate as platinum, to a substrate where it can only be formed using innovative methods, as is the case of gold. For the characterization of the graphene layers we have used in situ surface science techniques as low energy electron diffraction (LEED), auger electron spectroscopy (AES) and scanning tunneling microscopy (STM).One of the main advantages of our methodology is that low surface temperatures are required to form graphene. Thus, by annealing Pt(111) and Au(111) substrates up to 650 °C and 550 °C respectively during carbon evaporation, we have obtained the characteristic LEED diagrams commonly attributed to graphene on these surfaces. STM results further prove the formation of graphene. For the case of G on Pt(111), STM images show a long range ordering associated with moiré patterns that correspond to a monolayer of graphene on (111) platinum surface. On the other hand, G/Au(111) STM results reveal the formation of dendritic islands pinned to atomic step edges. This method opens up new possibilities for the formation of graphene on many different substrates with potential technological applications.     

Hydrogen Formation in the Reactions of Methanol on Supported Au Catalysts

The adsorption and reactions of methanol have been investigated on Au metal supported by various oxides and carbon Norit of high surface area. Infrared spectroscopic studies revealed the dissociation of methanol at 300 K, which mainly occurs on the oxide-supports yielding methoxy species. The presence of Au already appeared in the increased amounts of desorbed products in the TPD spectra. The reaction pathway of the decomposition and the activity of the catalyst sensitively depend on the nature of the support. As regards the production of hydrogen the most effective catalyst is Au/CeO₂ followed by Au/MgO, Au/TiO₂ and Au/Norit. In contrast, on Au/Al₂O₃ the main process is the dehydration reaction yielding dimethyl ether. On Au/CeO₂ the decomposition of methanol starts above ~500 K and approaches total conversion at 723–773 K. The products are H₂ (~68%) and CO (~27%) with very small amounts of methane and CO₂. The decomposition of methanol follows the first order kinetics. The activation energy of this process is 87.0 kJ/mol. The selectivity of H₂ formation at 573–773 K was ~90%, this value increased to 97% using CH₃OH:H₂O (1:1) reacting mixture indicating the involvement of water in the reaction. No deactivation of Au catalysts was experienced at 773 K in ~10 h. It is assumed that the interface between Au and partially reduced ceria is responsible for the high activity of Au/CeO₂ catalyst.     

Insights into the reactivity of supported Au nanoparticles: combining theory and experiments

The origin of the extraordinary catalytic activity of gold nanoparticles is discussed on the basis of density-functional calculations, adsorption studies on single crystal surfaces, and activity measurements on well characterized supported gold particles. A number of factors are identified contributing to the activity, and it is suggested that it is useful to consider low-coordinated Au atoms as the active sites, for example, CO oxidation and that the effect of the support can be viewed as structural and electronic promotion. We identify the adsorption energy of oxygen and the Au-support interface energy as important parameters determining the catalytic activity.     

Comparative study of Au/ZrO2 catalysts in CO oxidation and 1,3-butadiene hydrogenation

This work investigates the effects of Au³⁺/Au⁰ ratio or distribution of gold oxidation states in Au/ZrO₂ catalysts of different gold loadings (0.01–0.76% Au) on CO oxidation and 1,3-butadiene hydrogenation by regulating the temperature of catalyst calcination (393–673 K) and pre-reduction with hydrogen (473–523 K). The catalysts were prepared by deposition–precipitation and were characterized with elemental analysis, nitrogen adsorption/desorption, TEM, XPS and TPR. The catalytic data showed that the exposed metallic Au⁰ atoms at the surface of Au particles were not the only catalytic sites for the two reactions, isolated Au³⁺ ions at the surface of ZrO₂, such as those in the catalysts containing no more than 0.08% Au were more active by TOF. For 0.76% Au/ZrO₂ catalysts having coexisting Au³⁺ and Au⁰, the catalytic activity changed differently with varying the Au³⁺/Au⁰ ratio in the two reactions. The highest activity for the CO oxidation reaction was observed over the catalyst of Au³⁺/Au⁰ = 0.33. However, catalyst with a higher Au³⁺/Au⁰ ratio showed always a higher activity for the hydrogenation reaction; co-existance of Au⁰ with Au³⁺ ions lowered the catalyst activity. Moreover, the coexisting Au particles changed the product selectivity of 1,3-butadiene hydrogenation to favor the formation of more trans-2-butene and butane. It is thus suggested that for better control of the catalytic performance of Au catalyst the effect of Au³⁺/Au⁰ ratio on catalytic reactions should be investigated in combination with the particle size effect of Au.     

Scanning probe microscopy study of chemical vapor deposition grown graphene transferred to Au(111)

Graphene is grown by chemical vapor deposition (CVD) on copper films and transferred ex situ to atomically flat Au(111) films, after which the sample is annealed in ultra-high vacuum (UHV) prior to scanning tunneling microscopy (STM) investigation. STM imaging at 78 K reveals large, clean and defect-free atomically flat areas that are separated by graphene wrinkles and grain boundaries. In addition to the graphene atomic structure, the flat surface regions exhibit patterns with larger periodicity that can be interpreted as Moiré patterns formed by the atomic lattices of the graphene and the gold. Our findings show that the CVD growth and ex situ transfer of graphene (G) to atomically flat Au(111) surfaces allows obtaining clean and high-quality G/Au surfaces that are suitable for in situ deposition of, e.g., molecules and atoms, for UHV investigation purposes. This approach may offer a higher degree of freedom in preparing bare and doped graphene on atomically flat surfaces compared to a full in situ approach.     

The kinetics of CO oxidation by adsorbed oxygen on well‐defined gold particles on TiO2(110)

Very tiny Au particles on TiO₂ show excellent activity and selectivity in a number of oxidation reactions. We have studied the vapor deposition of Au onto a TiO₂(110) surface using XPS, LEIS, LEED and TPD and found that we can prepare Au islands with controlled thicknesses from one to several monolayers. In order to understand at the atomic level the unusual catalytic activity in oxidation reactions of this system, we have studied oxygen adsorption on Au/TiO₂(110) as a function of Au island thickness, and have measured the titration of this adsorbed oxygen with CO gas to yield CO₂, as function of Au island thickness, CO pressure and temperature. A hot filament was used to dose gaseous oxygen atoms. TPD results show higher O₂ desorption temperatures (741 K) from ultrathin gold particles on TiO₂(110) than from thicker particles (545 K). This implies that O_a bonds much more strongly to ultrathin islands of Au. Thus from Brønsted relations, ultrathin gold particles should be able to dissociatively adsorb O₂ more readily than thick gold particles. Our studies of the titration reaction of oxygen adatoms with CO (to produce CO₂) show that this reaction is extremely rapid at room temperature, but its rate is slightly slower for the thinnest Au islands. Thus the association reaction (CO_g + O_a → CO_2,g) gets faster as the oxygen adsorption strength decreases, again as expected from Brønsted relations. For islands of about two atomic layers thickness, the rate increases slowly with temperature, with an apparent activation energy of 11.4 ± 2.8 kJ/mol, and shows a first‐order rate in CO pressure and oxygen coverage, similar to bulk Au(110).     

Electrooxidation of d- and l-Glucose at Well-Defined Chiral Bimetallic Electrodes

The electrooxidation of d- and l-glucose at chiral Pt{321}^r/s single crystal electrodes modified with Au, Ag and Bi adatoms up to a coverage of one monolayer (ML) is reported. All adatoms investigated are found to selectively decorate kink and step sites. Only at higher coverages is adsorption onto the narrow {111} terrace sites observed for Bi, Ag and Au, consistent with previously reported adsorption behaviour on stepped surfaces vicinal to the {111} plane for chemisorbates exhibiting a lower work function than platinum. However, silver is found to block {111} terrace sites even when Pt step sites are still available on Pt{321}. This behaviour is ascribed to the propensity of silver to undergo place-exchange to form a surface alloy. The selective decoration of chiral kink sites has a profound influence on the voltammetric response of Pt{321} towards glucose electrooxidation. For bismuth adsorption, the electrooxidation current density initially increases and reaches a maximum when bismuth adsorption at {111} terraces commences. This is because the reaction pathways at step/kink sites leading to the formation of adsorbed CO (a surface poison for the clean surface reaction) and other strongly adsorbed intermediates, are either blocked by adsorbed bismuth or their electrooxidation and subsequent removal promoted. Once all step/kink sites are blocked by bismuth, hardly any chiral discrimination can be discerned between r-/s-electrodes towards d-/l-glucose. Silver adsorption does not cause any increase in glucose electrooxidation current density but rather induces a continual attenuation in glucose electrooxidation activity, particular (in contrast to bismuth) electrooxidation current at potentials in excess of 0.35 V. Therefore, unlike for bismuth, the initial glucose adsorption and electrooxidation processes associated with chiral kink sites appear to be preserved even though silver adsorbs at these sites. It is speculated that spontaneous place-exchange of silver with platinum to form a PtAg surface alloy at steps is responsible for this difference in behaviour between silver and bismuth. Finally, gold neither promotes reaction rate nor preserves chiral discrimination and is therefore deduced to act as an inert site blocker (no alloying, no promotion of CO electrooxidation) leading to complete attenuation of glucose electrooxidation current at a coverage of one ML.     

Carbon Monoxide Oxidation over Au/Ce1−x Zr x O2 Catalysts: Effects of Moisture Content in the Reactant Gas and Catalyst Pretreatment

The Au/Ce_1?x Zr _x O₂ (x = 0, 0.25, 1) catalysts were synthesized, characterized by BET, XRD, TPR-H₂, HRTEM, AAS and tested in CO oxidation. The effect of moisture in the reactant gas on CO conversion has been studied in a wide range of concentrations (~0.7–6000 ppm). Moisture generates a positive effect on catalytic activity and wet conditions gave higher CO conversions. The optimum concentration of moisture for CO oxidation over Au/CeO₂ and Au/Ce_0.75Zr_0.25O₂ is 200–1000 ppm, while further increase in the moisture content suppresses CO conversion. The activity of the studied Au catalysts depends on the amount of moisture adsorbed on the catalyst rather than on its content in the feed stream, which suggests that the reaction involves water-derived species on the catalysts surface. The effect of the catalysts pretreatment in air, dry He, H₂ stream as well as H₂ + H₂O gas mixture on their catalytic performance in CO oxidation has been also investigated. The model of the active sites for CO oxidation over the studied catalysts was proposed.     

Electrocatalytic dioxygen reduction on underpotentially deposited Pb on Au(111) studied by an active site blocking strategy

Electrochemical measurements and in situ scanning tunneling microscopy (STM) are performed to establish a structure–reactivity correlation for peroxide or dioxygen reduction on underpotentially deposited (upd) Pb on Au(111) in 0.1 M HClO₄. While STM imaging reveals the presence of Pb islands with height of 0.25±0.05 nm at the potential of highest catalytic activity toward the O₂ and H₂O₂ reduction, the full Pb monolayer formed at −0.03 V vs. NHE shows about half the activity of the Pb islands. Ethanethiol (EtSH) significantly but not completely inhibits the H₂O₂ reduction activity of the Pb island structure. STM shows that EtSH introduction leads to the formation of a 0.13-nm-high terrace along the edges of the Pb islands, which is assigned to EtSH bound to the Au surface near the Pb islands with the alkyl chain oriented roughly perpendicular to the surface. These results show that edge sites around the Pb island are the active site of catalysis, though the sites atop the Pb islands may also take part in catalytic O₂ reduction by Pb upd on Au(111).     

Why Au and Cu Are More Selective Than Pt for Preferential Oxidation of CO at Low Temperature

Self-consistent, periodic density functional theory (DFT) calculations and micro-kinetic modeling are used to compare selectivity for the preferential oxidation of CO (PROX) with respect to H₂ based on studies of elementary reaction steps on the (111) facet of Au, Cu and Pt. The first step of H oxidation (OH formation) has a higher activation barrier than the second step (H₂O formation) on all three metal surfaces, indicating that OH formation competes with CO oxidation for the removal of trace amounts of CO from a typical reformate gas. The activation energy barrier for CO oxidation is found to be 0.18eV on Au(111), 0.82eV on Cu(111) and 0.96eV on Pt(111), whereas the barrier for OH formation is 0.90, 1.28 and 0.83eV respectively. A micro-kinetic model based on the DFT results shows that trends in the selectivity of these metals at different temperatures is due to (i) differences in the rate constants of the competitive CO and H oxidation reactions, and (ii) differences in the CO and H surface coverages. Our results explain why Au and Cu are more selective PROX catalysts compared to Pt at low temperatures. At higher temperatures, Pt and Cu lose some of their selectivity to CO oxidation, whereas the selectivity on Au decreases substantially primarily because of the significantly weaker CO adsorption.     

Gold Nanoparticles on Yttrium Modified Titania: Support Properties and Catalytic Activity

A series of titanium oxide catalysts modified with yttrium has been prepared by sol–gel method and their structural properties have been studied. The incorporation of yttrium in the titania lattice favors the formation of oxygen vacancies while at low Y loadings the anatase structure is preserved. The catalytic activity of these solids for CO oxidation is found to be significantly dependent on their physical properties. In particular the amount of dopant controls the number of surface oxygen vacancies created as well as the gold particle size, which directly affects the catalytic activity. Also, a linear relationship between the catalytic activity and the band gap values, which depend on the Y loading, is observed. Density functional theory based calculations show that Y atoms are incorporated at the TiO₂ surface at substitutional positions only, while the preferred oxygen vacancies arise by removing the bridge surface oxygen atoms. These O-vacancies are the preferential adsorption sites for Au atoms and nanoparticles, acting as nucleation centers that favor the dispersion of the catalyst active phase over the support surface. In agreement with experiment, Y doping is found to decrease the band gap of the support due to a destabilization of the valence band of the oxide.     

Deactivation of nanosize gold supported on zirconia in CO oxidation

An Au/ZrO₂ catalyst containing nanosize gold was investigated with respect to its activity in CO oxidation. The high initial activity observed at temperatures down to 230 K was followed by a gradual decrease. Two main reasons for the catalyst deactivation were found: (i) adsorption of CO and its accumulation as carbonates, this deactivation being reversible and after heating the catalyst surface being restored by CO₂ evolution, (ii) agglomeration of Au particles, which causes irreversible however weak deactivation. IR, XPS and TPD data were provided in support of a probable model of CO oxidation and deactivation on Au/ZrO₂ catalyst.     

Surface Modification of Pd/α-Si3N4 Catalysts Through the Solvent Used During Synthesis. Implications on the CO Chemisorption Properties and Catalytic Performances

Palladium catalysts supported on α-Si₃N₄ were prepared by impregnation with Pd(II)-acetate dissolved either in toluene or in water. The mean metal particle size of ~0.5 wt% Pd catalysts was similar (~5 nm) and independent of the way of preparation. Nevertheless, the two catalysts present very different chemisorption behaviour chemisorptive and catalytic properties. Fourier transformed infrared (FTIR) spectra of adsorbed CO at different temperatures (ranging from room temperature to 300 °C) show a very different behaviour for both catalysts. While the CO adsorption states on the Pd/α-Si₃N₄ prepared in toluene are very similar to those generally measured for silica and/or alumina supported palladium catalysts, CO chemisorbs less strongly on Pd/α-Si₃N₄ prepared in water and on different adsorption sites. The Pd/α-Si₃N₄ catalyst obtained by aqueous impregnation is much less efficient for the methane total oxidation. It is less active and less stable: it deactivates strongly after 3 h on stream at 650 °C. The two catalysts present about the same activity for the 1,3-butadiene hydrogenation after stabilisation at 20 °C. But, the catalyst prepared in water shows a much better selectivity to butenes. The results are discussed in terms of the possible migration of silicon atoms from the silicon nitride support to the surface of the palladium particles, when the catalyst is prepared in water. This is not the case when prepared in an organic solvent.