Activation of water on MnOx-nanocluster-modified rutile (110) and anatase (101) TiO2 and the role of cation reduction

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dc.contributor.author Rhatigan, Stephen
dc.contributor.author Nolan, Michael
dc.date.accessioned 2019-10-23T04:24:51Z
dc.date.available 2019-10-23T04:24:51Z
dc.date.issued 2019-02-12
dc.identifier.citation Rhatigan, S. and Nolan, M. (2019) 'Activation of Water on MnOx-Nanocluster-Modified Rutile (110) and Anatase (101) TiO2 and the Role of Cation Reduction', Frontiers in Chemistry, 7, 67. (12pp.) DOI: 10.3389/fchem.2019.00067 en
dc.identifier.volume 7 en
dc.identifier.startpage 1 en
dc.identifier.endpage 12 en
dc.identifier.uri http://hdl.handle.net/10468/8827
dc.identifier.doi 10.3389/fchem.2019.00067 en
dc.description.abstract Surface modification of titania surfaces with dispersed metal oxide nanoclusters has the potential to enhance photocatalytic activity. These modifications can induce visible light absorption and suppress charge carrier recombination which are vital in improving the efficiency. We have studied heterostructures of Mn4O6 nanoclusters modifying the TiO2 rutile (110) and anatase (101) surfaces using density functional theory (DFT) corrected for on-site Coulomb interactions (DFT + U). Such studies typically focus on the pristine surface, free of the point defects and surface hydroxyls present in real surfaces. In our study we have considered partial hydroxylation of the rutile and anatase surfaces and the role of cation reduction, via oxygen vacancy formation, and how this impacts on a variety of properties governing the photocatalytic performance such as nanocluster adsorption, light absorption, charge separation, and reducibility. Our results indicate that the modifiers adsorb strongly at the surface and that modification extends light absorption into the visible range. MnOx-modified titania can show an off-stoichiometric ground state, through oxygen vacancy formation and cation reduction spontaneously, and both modified rutile and anatase are highly reducible with moderate energy costs. Manganese ions are therefore present in a mixture of oxidation states. Photoexcited electrons and holes localize at cluster metal and oxygen sites, respectively. The interaction of water at the modified surfaces depends on the stoichiometry and spontaneous dissociation to surface bound hydroxyls is favored in the presence of oxygen vacancies and reduced metal cations. Comparisons with bare TiO2 and other TiO2-based photocatalyst materials are presented throughout. en
dc.description.sponsorship ERA.Net for Materials Research and Innovation (M-ERA.Net 2); SFI (Grant Number SFI/16/M-ERA/3418 RATOCAT) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Frontiers Media S.A. en
dc.relation.uri https://www.frontiersin.org/articles/10.3389/fchem.2019.00067/full
dc.rights ©2019 Rhatigan and Nolan. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms en
dc.rights.uri http://creativecommons.org/licenses/by/4.0/ en
dc.subject TiO2 en
dc.subject Water activation en
dc.subject Reduction en
dc.subject Oxygen vacancies en
dc.subject Photocatalysis en
dc.title Activation of water on MnOx-nanocluster-modified rutile (110) and anatase (101) TiO2 and the role of cation reduction en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Michael Nolan, Tyndall National Institute, University College Cork, Cork, Ireland. +353-21-490-3000 Email:michael.nolan@tyndall.ie en
dc.internal.availability Full text available en
dc.description.version Published Version en
dc.contributor.funder Science Foundation Ireland en
dc.contributor.funder Horizon 2020 en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Frontiers in Chemistry en
dc.internal.IRISemailaddress michael.nolan@tyndall.ie en
dc.identifier.articleid 67 en
dc.relation.project info:eu-repo/grantAgreement/SFI/SFI US Ireland R&D Partnership/14/US/E2915/IE/SusChEM: Using theory-driven design to tailor novel nanocomposite oxides for solar fuel production/ en
dc.relation.project info:eu-repo/grantAgreement/EC/H2020::ERA-NET-Cofund/685451/EU/ERA-NET for materials research and innovation/M-ERA.NET 2 en
dc.relation.project info:eu-repo/grantAgreement/EC/H2020::ERA-NET-Cofund/685451/EU/ERA-NET for materials research and innovation/M-ERA.NET 2 en
dc.identifier.eissn 2296-2646


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©2019 Rhatigan and Nolan. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms Except where otherwise noted, this item's license is described as ©2019 Rhatigan and Nolan. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms
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