CO Oxidation on Supported Single Pt Atoms: Experimental and ab Initio Density Functional Studies of CO Interaction with Pt Atom on ϑ-AlO(010) Surface.
Although there are only a few known examples of supported single-atom catalysts, they are unique because they bridge the gap between homogeneous and heterogeneous catalysis. Here, we report the CO oxidation activity of monodisperse single Pt atoms supported on an inert substrate, ϑ-alumina (AlO), in...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 34; pp. 12634 - 12646 |
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| Autores principales: | , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
8/28/2013
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| 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=90269404&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 90269404 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: 8/28/2013 vid: 135 iid: 34 pid: 997 pub: American Chemical Society artinfo: ui: 90269404 10.1021/ja401847c ppf: 12634 ppct: 12 formats: tig: atl: CO Oxidation on Supported Single Pt Atoms: Experimental and ab Initio Density Functional Studies of CO Interaction with Pt Atom on ϑ-AlO(010) Surface. aug: au: Moses-DeBusk, Melanie Mina Yoon Allard, Lawrence F. Mullins, David R. Zili Wu Xiaofan Yang Veith, Gabriel Malcolm Stocks, G. Narula, Chaitanya K. affil: Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6133, United States Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6133, United States Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6133, United States su: Oxidation of carbon monoxide Platinum catalysts Aluminum oxide Ab initio quantum chemistry methods Carbonates Metal bonding sug: subj: Oxidation of carbon monoxide Platinum catalysts Aluminum oxide Ab initio quantum chemistry methods Carbonates Metal bonding ab: Although there are only a few known examples of supported single-atom catalysts, they are unique because they bridge the gap between homogeneous and heterogeneous catalysis. Here, we report the CO oxidation activity of monodisperse single Pt atoms supported on an inert substrate, ϑ-alumina (AlO), in the presence of stoichiometric oxygen. Since CO oxidation on single Pt atoms cannot occur via a conventional Langmuir-Hinshelwood scheme (L-H scheme) which requires at least one Pt-Pt bond, we carried out a first-principles density functional theoretical study of a proposed pathway which is a variation on the conventional L-H scheme and inspired by the organometallic chemistry of platinum. We find that a single supported Pt atom prefers to bond to O over CO. CO then bonds with the oxygenated Pt atom and forms a carbonate which dissociates to liberate CO, leaving an oxygen atom on Pt. Subsequent reaction with another CO molecule regenerates the single-atom catalyst. The energetics of the proposed mechanism suggests that the single Pt atoms will get covered with CO unless the temperature is raised to eliminate CO. We find evidence for CO coverage at room temperature supporting the proposed mechanism in an in situ diffuse reflectance infrared study of CO adsorption on the catalyst's supported single atoms. Thus, our results clearly show that supported Pt single atoms are catalytically active and that this catalytic activity can occur without involving the substrate. Characterization by electron microscopy and X-ray absorption studies of the monodisperse Pt/ϑ-AlO are also presented. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
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