Role of Au–C Interactions on the Catalytic Activity of Au Nanoparticles Supported on TiC(001) toward Molecular Oxygen Dissociation.
High-resolution photoemission and density functional calculations on realistic slab surface models were used to study the interaction and subsequent dissociation of O with Au nanoparticles supported on TIC(001). The photoemission results indicate that at 150 K O adsorbs molecularly on the supported...
| Published in: | Journal of the American Chemical Society Vol. 132; no. 9; pp. 3177 - 3187 |
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| Main Authors: | , , , , , |
| Format: | Article |
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American Chemical Society
3/10/2010
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=50318867&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 50318867 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 3/10/2010 vid: 132 iid: 9 pid: 997 pub: American Chemical Society artinfo: ui: 50318867 10.1021/ja910146g ppf: 3177 ppct: 10 formats: tig: atl: Role of Au–C Interactions on the Catalytic Activity of Au Nanoparticles Supported on TiC(001) toward Molecular Oxygen Dissociation. aug: au: Rodríguez, José A. Feria, Leticia Jirsak, Tomas Takahashi, Yoshiro Nakamura, Kenichi Illas, Francesc affil: Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973 Departament de Química Física & institut de Qulmica Teôrica i Computacional (1QTCUB), Universitat de Barcelona, C/Martí i Fran quës 1, 08028 Barcelona, Spain Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503, Japan su: Gold isotopes Nanoparticles Dissociation (Chemistry) Titanium carbide Oxygen Photoemission Reactivity (Chemistry) Atoms sug: subj: Gold isotopes Nanoparticles Dissociation (Chemistry) Titanium carbide Oxygen Photoemission Reactivity (Chemistry) Atoms ab: High-resolution photoemission and density functional calculations on realistic slab surface models were used to study the interaction and subsequent dissociation of O with Au nanoparticles supported on TIC(001). The photoemission results indicate that at 150 K O adsorbs molecularly on the supported gold nanoparticles, and upon heating to temperatures above 200 K the O → 20 reaction takes place with migration of atomic oxygen to the TiC(001) substrate. The addition of Au to TiC(001) substantially enhances the rate of O dissociation at room temperature. The reactivity of Au nanoparticles supported on TiC(001) toward O dissociation is much larger than that of similar nanoparticles supported either on TiO(110) or MgO(001) surfaces, where the cleavage of 0-0 bonds is very difficult. Density functional calculations carried out on large supercells show that the contact of Au with TiC(001) is essential for charge polarization and an enhancement in the chemical activity of Au. Small two-dimensional particles which expose Au atoms in contact with TiC(001) are the most reactive. While O prefers binding to Au sites, the 0 atoms interact more strongly with the TiC(001) surface. The oxygen species active during the low-temperature (<200 K) oxidation of carbon monoxide on Au/TiC(001) is chemisorbed O. Once atomic 0 binds to TiC(001), the chemisorption bond is so strong that temperatures well above 400 K are necessary to remove the 0 adatoms from the TiC(001) substrate by direct reaction with CO. The high reactivity of Au/TiC(001) toward O at low-temperature opens the route for the transformation of alcohols and amines on the supported Au nanoparticles. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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