H2_2 dissociation over Au-nanowires and the fractional conductance quantum

The dissociation of H$_2$ molecules on stretched Au nanowires and its effect on the nanowire conductance are analyzed using a combination of Density Functional (DFT) total energy calculations and non-equilibrium Keldish-Green function methods. Our DFT simulations reproduce the characteristic formation of Au monoatomic chains with a conductance close to % the conductance quantum $G_0 = 2e^2/h$. These stretched Au nanowires are shown to be better catalysts for H$_2$ dissociation than Au surfaces. This is confirmed by the nanowire conductance evidence: while not affected practically by molecular hydrogen, atomic hydrogen induces the appearance of fractional conductances ($G \sim 0.5 G_0$) as observed experimentally.Comment: 4 pages, 3 figure

Adsorption and Diffusion of Pt and Au on the Stoichiometric and Reduced TiO2 Rutile (110) Surfaces

A comparative first principles pseudopotential study of the adsorption and migration profiles of single Pt and Au atoms on the stoichiometric and reduced TiO2 rutile (110) surfaces is presented. Pt and Au behave similarly with respect to (i) most favorable adsorption sites, which are found to be the hollow and substitutional sites on the stoichiometric and reduced surfaces, respectively, (ii) the large increase in their binding energy (by ~1.7 eV) when the surface is reduced, and (iii) their low migration barrier near 0.15 eV on the stoichiometric surface. Pt, on the other hand, binds more strongly (by ~2 eV) to both surfaces. On the stoichiometric surface, Pt migration pattern is expected to be one-dimensional, which is primarily influenced by interactions with O atoms. Au migration is expected to be two-dimensional, with Au-Ti interactions playing a more important role. On the reduced surface, the migration barrier for Pt diffusion is significantly larger compared to Au.Comment: 3 figures, 1 table, submitted to PR

Au/TiO2(110) interfacial reconstruction stability from ab initio

We determine the stability and properties of interfaces of low-index Au surfaces adhered to TiO2(110), using density functional theory energy density calculations. We consider Au(100) and Au(111) epitaxies on rutile TiO2(110) surface, as observed in experiments. For each epitaxy, we consider several different interfaces: Au(111)//TiO2(110) and Au(100)//TiO2(110), with and without bridging oxygen, Au(111) on 1x2 added-row TiO2(110) reconstruction, and Au(111) on a proposed 1x2 TiO reconstruction. The density functional theory energy density method computes the energy changes on each of the atoms while forming the interface, and evaluates the work of adhesion to determine the equilibrium interfacial structure.Comment: 20 pages, 11 figure

Reaction mechanism of the direct gas phase synthesis of H2O2 catalyzed by Au3

The gas phase reaction of molecular oxygen and hydrogen catalyzed by a Au3cluster to yield H2O2 was investigated theoretically using second order Z-averaged perturbation theory, with the final energies obtained with the fully size extensive completely renormalized CR-CC(2,3) coupled clustertheory. The proposed reaction mechanism is initiated by adsorption and activation of O2 on the Au3cluster. Molecular hydrogen then binds to the Au3O2 global minimum without an energy barrier. The reaction between the activated oxygen and hydrogen molecules proceeds through formation of hydroperoxide (HO2) and a hydrogen atom, which subsequently react to form the product hydrogen peroxide. All reactants, intermediates, and product remain bound to the goldcluster throughout the course of the reaction. The steps in the proposed reaction mechanism have low activation energy barriers below 15kcal∕mol. The overall reaction is highly exothermic by ∼30kcal∕mol

Homogeneous Gold Catalysis through Relativistic Effects: Addition of Water to Propyne

In the catalytic addition of water to propyne the Au(III) catalyst is not stable under non-relativistic conditions and dissociates into a Au(I) compound and Cl2. This implies that one link in the chain of events in the catalytic cycle is broken and relativity may well be seen as the reason why Au(III) compounds are effective catalysts.Comment: 12 pages, 3 figures, 1 tabl

Speciation-controlled incipient wetness impregnation: A rational synthetic approach to prepare sub-nanosized and highly active ceria–zirconia supported gold catalysts

On the basis of calculated thermodynamic species distribution diagrams and by appropriately controlling the pH of aqueous HAuCl4 solutions, it has been possible to prepare, using a Speciation-controlled Incipient Wetness Impregnation (ScIWI) approach, Au catalysts supported on ceria–zirconia mixed oxides featuring both high gold loadings and excellent metal dispersions. This rational synthesis method is carried out at room temperature. It is both much simpler, in equipment terms, and less expensive than widely used Deposition–Precipitation (DP). Moreover, the use of ScIWI allows overcoming the severe limitations of previously assayed impregnation methods. With this procedure it is possible to prepare active catalysts in CO oxidation with high efficiency in terms of gold precursor usage, i.e. minimizing Au losses during synthesis. Therefore this, quite amenable, novel strategy for the facile preparation of highly dispersed supported gold catalysts gathers the necessary requirements for both its use at lab scale and an easy scaling-up to industrial levels

Identifying the Azobenzene/Aniline reaction intermediate on TiO2-(110) : a DFT Study

Density functional theory (DFT) calculations, both with and without dispersion corrections, have been performed to investigate the nature of the common surface reaction intermediate that has been shown to exist on TiO2(110) as a result of exposure to either azobenzene (C6H5N═NC6H5) or aniline (C6H5NH2). Our results confirm the results of a previous DFT study that dissociation of azobenzene into two adsorbed phenyl imide (C6H5N) fragments, as was originally proposed, is not energetically favorable. We also find that deprotonation of aniline to produce this surface species is even more strongly energetically disfavored. A range of alternative surface species has been considered, and while dissociation of azobenzene to form surface C6H4NH species is energetically favored, the same surface species cannot form from adsorbed aniline. On the contrary, adsorbed aniline is much the most stable surface species. Comparisons with experimental determinations of the local adsorption site, the Ti–N bond length, the molecular orientation, and the associated C 1s and N 1s photoelectron core level shifts are all consistent with the DFT results for adsorbed aniline and are inconsistent with other adsorbed species considered. Possible mechanisms for the hydrogenation of azobenzene required to produce this surface species are discussed