CO Oxidation on TiO (110) Supported Subnanometer Gold Clusters: Size and Shape Effects.
We performed a comprehensive study of catalytic activities of subnanometer Au clusters supported on TiO(110) surface (Au/TiO, n = 1–4, 7, 16–20) by means of density functional theory (DFT) calculations and microkinetics analysis. The creditability of the chosen DFT/microkienetics methodologies was d...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 51; pp. 19336 - 19347 |
|---|---|
| Autores principales: | , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
12/25/2013
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=93733849&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 93733849 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: 12/25/2013 vid: 135 iid: 51 pid: 997 pub: American Chemical Society artinfo: ui: 93733849 10.1021/ja410292s ppf: 19336 ppct: 11 formats: tig: atl: CO Oxidation on TiO (110) Supported Subnanometer Gold Clusters: Size and Shape Effects. aug: au: Lei Li Yi Gao Hui Li Yu Zhao Yong Pei Zhongfang Chen Xiao Cheng Zeng affil: Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588, United States Laboratory of Physical Biology and Division of Interfacial Water, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Hunan Province 411105, China Department of Chemistry, University of Puerto Rico, San Juan, Puerto Rico 00931 su: Surface chemistry Chemical kinetics Statistical hypothesis testing Density functionals Physical & theoretical chemistry sug: subj: Surface chemistry Chemical kinetics Statistical hypothesis testing Density functionals Physical & theoretical chemistry ab: We performed a comprehensive study of catalytic activities of subnanometer Au clusters supported on TiO(110) surface (Au/TiO, n = 1–4, 7, 16–20) by means of density functional theory (DFT) calculations and microkinetics analysis. The creditability of the chosen DFT/microkienetics methodologies was demonstrated by the very good agreement between predicted catalytic activities with experimental measurement (J. Am. Chem. Soc, 2004, 126, 5682–5483) for the Au/TiO and Au/TiO benchmark systems. For the first time, the size- and shape-dependent catalytic activities of the subnanometer Au clusters (Au–Au) on TiO supports were systematically investigated. We found that catalytic activities of the Au/TiO systems increase with the size n up to Au, for which the hollow-cage Au isomer exhibits highest activity for the CO oxidation, with a reaction rate 30 times higher than that of Au/TiO system. In stark contrast, the pyramidal isomer of Au exhibits much lower activity comparable to the Au/TiO systems. Moreover, we found that the hollow-cage Au is robust upon the soft-landing with an impact velocity of 200 m/s to the TiO substrate, and also exhibits thermal stability upon CO and O co-adsorption. The larger pyramidal Au and Au clusters (on the TiO support) display much lower reaction rates than the pyramidal Au. Results of rate of reactions for unsupported (gas-phase) and supported Au clusters can be correlated by a contour plot that illustrates the dependence of the reaction rates on the CO and O adsorption energies. With the TiO support, however, the catalytic activities can be greatly enhanced due to the weaker adsorption of CO on the TiO support than on the Au clusters, thereby not only the ratio of O/CO adsorption energy and the probability for the O to occupy the Ti sites are increased but also the requirement for meeting the critical line becomes weaker. The obtained contour plot not only can provide guidance for the theoretical investigation of catalytic activity on other metal cluster/support systems, but also assist experimental design of optimal metal cluster/support systems to achieve higher catalytic efficiency. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
|---|