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What Controls Photocatalytic Water Oxidation on Rutile TiO2(110) under Ultra-High-Vacuum Conditions?
Migani, Annapaola (Institut Català de Nanociència i Nanotecnologia)
Blancafort, Lluís (Institut de Química Computacional i Catàlisi)

Date: 2017
Abstract: The photocatalytic O-H dissociation of water absorbed on a rutile TiO(110) surface in ultrahigh vacuum (UHV) is studied with spin-polarized density functional theory and a hybrid exchange-correlation functional (HSE06), treating the excited-state species as excitons with triplet multiplicity. This system is a model for the photocatalytic oxidation of water by TiO in an aqueous medium, which is relevant for the oxygen evolution reaction and photodegradation of organic pollutants. We provide a comprehensive mechanistic picture where the most representative paths correspond to excitonic configurations with the hole located on three- and two-coordinate surface oxygen atoms (O and O). Our picture explains the formation of the species observed experimentally. At near band gap excitation, the O path leads to the generation of hydroxyl anions which diffuse on the surface, without net oxidation. In contrast, free hydroxyl radicals are formed at supra band gap excitation (e. g. , 266 nm) from an interfacial exciton that undergoes O-H dissociation. The oxidation efficiency is low because the path associated with the O exciton, which is the most favored one thermodynamically, is unreactive because of a high propensity for charge recombination. Our results are also relevant to understand the reactivity in the liquid phase. We assign the photoluminescence measured for atomically flat TiO(110) surfaces in an aqueous medium to the O exciton, in line with the proposal based on experiments, and we have identified a species derived from the O exciton with an activated O-Ti bond that may be relevant in photocatalytic applications in an aqueous medium.
Note: This is an open access article published under an ACS AuthorChoice License. See Standard ACS AuthorChoice/Editors' Choice Usage Agreement - https://pubs.acs.org/page/policy/authorchoice_termsofuse.html
Note: Número d'acord de subvenció MINECO/UNGI10-4E-801
Note: Número d'acord de subvenció MINECO/RYC-2011-09582
Note: Número d'acord de subvenció MINECO/CTQ-2015-69363-P
Note: Número d'acord de subvenció AGAUR/2014/SGR-1202
Rights: Tots els drets reservats.
Language: Anglès
Document: article ; recerca ; publishedVersion
Subject: Band-gap excitation ; Charge recombinations ; Free hydroxyl radicals ; Oxidation efficiency ; Oxygen evolution reaction ; Photocatalytic application ; Photocatalytic oxidations ; Spin-polarized density functional theory
Published in: Journal of the American Chemical Society, Vol. 139, Issue 34 (August 2017) , p. 11845-11856, ISSN 1520-5126

DOI: 10.1021/jacs.7b05121

12 p, 3.5 MB

The record appears in these collections:
Research literature > UAB research groups literature > Research Centres and Groups (scientific output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles

 Record created 2019-07-26, last modified 2020-11-07

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