Coadsorption of CO and O2 on small free gold cluster anions at cryogenic temperatures: Model complexes for catalytic CO oxidation

Hagen, Jan; Socaciu, Liana D.; Elijazyfer, Maryam; Heiz, Ueli; Bernhardt, Thorsten M.; Wöste, L.

doi:10.1039/b201236g

Cited by 161 publications

(161 citation statements)

References 18 publications

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“…Such a cooperative effect has been observed experimentally for the reactivity of CO and O 2 when they are simultaneously adsorbed on the anionic Au clusters. 22,73 For a given cluster size, the electron affinities of the Ag clusters are smaller than the ones of the Au clusters. 61,62 Since electron affinity is a measure of the tendency of the cluster to accept an electron we predict that propene will bind more weakly to Ag n than Au n .…”

Section: ͑1͒mentioning

confidence: 99%

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Chrétien

Gordon

Metiu

2004

The Journal of Chemical Physics

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We use density functional theory(DFT) to investigate the bonding of propene to small gas-phase gold clusters and to a Au(111) surface. The desorption energy trends and the geometry of the binding sites are consistent with the following set of rules.(1) The bond of propene to gold is formed by donation of electron density from the highest occupied molecular orbital (HOMO) of propene to one of the low-lying empty orbitals [denoted by LUMO1, LUMO2, … (LUMO-lowest unoccupied molecular orbital)] of the gold cluster. (2) Propene binds to a site on the Au cluster where one of the low-lying LUMOs protrudes in the vacuum. Different isomers (same cluster, but different binding sites for propene) correspond to sites where different low-lying LUMOs protrude in space. (3) The desorption energy of the lowest energy isomer correlates with the energy of the lowest empty orbital of the cluster; the lower the energy of that LUMO, the higher the desorption energy. (4) If the lowest-lying LUMO protrudes into space at two nonequivalent sites at the edge of a cluster, propene binds more strongly to the site with the lowest coordination. These rules are consistent with the calculated bond energies and geometries for [Aun(C3H6)]q, for n=1−5 and n=8 and q=−1, 0, +1. Based on them we have made a number of predictions that have been confirmed by DFT calculations. The bond of propene to gold is strengthened as the net charge of the cluster varies from −1, to zero, to +1. Compared to a gas-phase cluster, a cluster on a support binds propene more strongly if the support takes electron density from the cluster (e.g., a Au cluster on a goldsurface) and more weakly if the support donates electron density to the cluster (e.g., a Au cluster on an oxygen vacancy on an oxide surface). KeywordsGold, Binding sites, Density functional theory, Desorption, Oxide surfaces Disciplines Chemistry CommentsThe following article appeared in Journal of Chemical Physics 121 (2004) We use density functional theory ͑DFT͒ to investigate the bonding of propene to small gas-phase gold clusters and to a Au͑111͒ surface. The desorption energy trends and the geometry of the binding sites are consistent with the following set of rules. ͑1͒ The bond of propene to gold is formed by donation of electron density from the highest occupied molecular orbital ͑HOMO͒ of propene to one of the low-lying empty orbitals ͓denoted by LUMO1, LUMO2, ... ͑LUMO-lowest unoccupied molecular orbital͔͒ of the gold cluster. ͑2͒ Propene binds to a site on the Au cluster where one of the low-lying LUMOs protrudes in the vacuum. Different isomers ͑same cluster, but different binding sites for propene͒ correspond to sites where different low-lying LUMOs protrude in space. ͑3͒ The desorption energy of the lowest energy isomer correlates with the energy of the lowest empty orbital of the cluster; the lower the energy of that LUMO, the higher the desorption energy. ͑4͒ If the lowest-lying LUMO protrudes into space at two nonequivalent sites at the edge of a cluster, propene binds more strong...

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Section: ͑1͒mentioning

confidence: 99%

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Chrétien

Gordon

Metiu

2004

The Journal of Chemical Physics

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“…These studies have shown that using ionic clusters as models can prove beneficial toward unraveling mechanistic information. It also has been shown that through the study of clusters, complete catalytic cycles may be identified and investigated in the gas phase (161,199,200).…”

Section: ϫmentioning

confidence: 99%

Clusters: A bridge across the disciplines of physics and chemistry

Jena

Castleman

2006

Proc. Natl. Acad. Sci. U.S.A.

227

161

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“…The surface negative charge decreases with the size of the Au clusters. Anionic Au atoms in the cluster have a stronger interaction with O 2 than a neutral Au atom [20,63,[86][87][88][89][90][91][92][93][94][95]. These findings suggest that the active sites for oxygenation on the supported and unsupported Au catalysts [63,93,96] are Au atoms which are negatively charged.…”

Section: Introductionmentioning

confidence: 62%

O2 dissociation in Na-modified gold ultrathin layer on Cu(111)

Politanoa

Chiarello

2010

Gold Bull

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High-resolution electron energy loss spectroscopy has been used to investigate the catalytic properties of Na-doped Au monolayer grown on Cu(111). The presence of Na atoms allows the dissociation of oxygen molecules and the stabilization of atomic oxygen. The strong reduction of the dissociation barrier for O 2 promoted by Na could readily favor many surface chemical reactions, due to the key role of atomic oxygen in many oxidation processes catalyzed by gold.

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Coadsorption of CO and O2 on small free gold cluster anions at cryogenic temperatures: Model complexes for catalytic CO oxidation

Cited by 161 publications

References 18 publications

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Binding of propene on small gold clusters and on Au(111): Simple rules for binding sites and relative binding energies

Clusters: A bridge across the disciplines of physics and chemistry

O2 dissociation in Na-modified gold ultrathin layer on Cu(111)

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