A Systematic Study of the Structure and Bonding of Halogens on Low-Index Transition Metal Surfaces

Migani, Annapaola; Illas, Francesc

doi:10.1021/jp060400u

Cited by 105 publications

(133 citation statements)

References 135 publications

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“…As in previous reports, 49 DFT methods predict lattice constants in very good agreement with experimentally measured values. The functional that provided the best overall results for the six metals was the PBE functional, and therefore the PBE functional was used in most of the subsequent calculations.…”

Section: A Methods: Bulk Propertiessupporting

confidence: 88%

Density functional theory study of mercury adsorption on metal surfaces

Steckel

2008

Phys. Rev. B

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Density functional theory ͑DFT͒ calculations are used to characterize the interaction of mercury with copper, nickel, palladium, platinum, silver, and gold surfaces. Mercury binds relatively strongly to all the metal surfaces studied, with binding energies up to ϳ1 eV for Pt and Pd. DFT calculations underestimate the energy of adsorption with respect to available experimental data. Plane-wave DFT results using the local density approximation and the Perdew-Wang 1991 and Perdew-Burke-Ernzerhof parametrizations of the generalized gradient approximation indicate that binding of mercury at hollow sites is preferred over binding at top or bridge sites. The interaction with mercury in order of increasing reactivity over the six metals studied is Ag Ͻ AuϽ CuϽ NiϽ PtϽ Pd. Binding is stronger on the ͑001͒ faces of the metal surfaces, where mercury is situated in fourfold hollow sites as opposed to the threefold hollow sites on ͑111͒ faces. In general, mercury adsorption leads to decreases in the work function; adsorbate-induced work function changes are particularly dramatic on Pt.

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Section: A Methods: Bulk Propertiessupporting

confidence: 88%

Density functional theory study of mercury adsorption on metal surfaces

Steckel

2008

Phys. Rev. B

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“…At both tested coverages of Cl, the Au-Cl interaction is stronger on the adatom covered surface, but when taking into account the cost of creating the adatomcovered surface, the 0.33 ML chlorine overlayer is lowest in energy while at 0.67 ML of chlorine, the adatom covered surfaces are lowest in energy. Other groups have performed important calculations of Cl on gold surfaces, but gold incorporation was not considered, which could have important implications on their results as discussed above for O [133][134][135][136]. However, Peljhan and Kokalj did allow metal incorporation for Cl adsorption on Cu (111) and they found many of the same trends [137].…”

Section: Release Of Au Upon Adsorption Of Electronegative Elements Onmentioning

confidence: 99%

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

2010

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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.

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“…This remarkable behaviour of silver allows the development of low specific energy consumption processes, thanks to the concomitant reduction of cell voltage and increase in current efficiency and substrate conversion. It is assumed to be linked with the well-known specific interactions of silver with halide anions [11][12][13][14], which, in turn, are governed by the Ag surface state and its modifications in dependence on the composition of the reaction medium (i.e. the halide leaving group, the structure of the organic moiety, the solvent and the supporting electrolyte).…”

Section: Introductionmentioning

confidence: 99%

Cavity microelectrodes for the voltammetric investigation of electrocatalysts: the electroreduction of volatile organic halides on micro-sized silver powders

et al. 2008

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In this work the use of cavity-microelectrodes is described for the study of the electrocatalytic properties of silver powders in the electroreduction of trichloromethane, taken as model compound. The key role played by the Ag surface status has driven the research towards the use of micro-and nanosized materials, whose exploitation requires the full understanding of the complex behaviour of multiphasial interfaces, and the development of the appropriate investigation methodologies. Moreover, comparison with electrodeposited silver macroelectrodes demonstrates the advantages of using cavity-microelectrodes, especially in terms of improvement of the electrocatalytic activity, insignificance of ohmic drop and double layer capacitance in the voltammetric response, and simplicity offered by the experimental procedure for renovating the electrode material and surface.

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A Systematic Study of the Structure and Bonding of Halogens on Low-Index Transition Metal Surfaces

Cited by 105 publications

References 135 publications

Density functional theory study of mercury adsorption on metal surfaces

Density functional theory study of mercury adsorption on metal surfaces

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

Cavity microelectrodes for the voltammetric investigation of electrocatalysts: the electroreduction of volatile organic halides on micro-sized silver powders

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