Chemical Dynamics of the First Proton-Coupled Electron Transfer of Water Oxidation on TiO Anatase.
Titanium dioxide (TiO) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron t...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 50; pp. 18774 - 18778 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
12/18/2013
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| 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=93405067&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 93405067 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: 12/18/2013 vid: 135 iid: 50 pid: 997 pub: American Chemical Society artinfo: ui: 93405067 10.1021/ja410685m ppf: 18774 ppct: 4 formats: tig: atl: Chemical Dynamics of the First Proton-Coupled Electron Transfer of Water Oxidation on TiO Anatase. aug: au: Jia Chen Ye-Fei Li Sit, Patrick Selloni, Annabella affil: Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States su: Density functional theory Titanium dioxide Water Interface dynamics Oxygen evolution reactions Photocatalysts Proton transfer reactions Molecular dynamics sug: subj: Density functional theory Titanium dioxide Water Interface dynamics Oxygen evolution reactions Photocatalysts Proton transfer reactions Molecular dynamics ab: Titanium dioxide (TiO) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO. We use a periodic model of the TiO/water interface that includes a slab of anatase TiO and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer. 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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