Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

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dc.contributor.author Iwaszuk, Anna
dc.contributor.author Nolan, Michael
dc.date.accessioned 2016-07-22T09:06:20Z
dc.date.available 2016-07-22T09:06:20Z
dc.date.issued 2013-05-09
dc.identifier.citation Iwaszuk, A. and Nolan, M. (2013) 'Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state', Catalysis Science & Technology, 3(8), pp. 2000-2008. http://dx.doi.org/10.1039/C3CY00194F en
dc.identifier.volume 3 en
dc.identifier.issued 8 en
dc.identifier.startpage 2000 en
dc.identifier.endpage 2008 en
dc.identifier.issn 2044-4753
dc.identifier.issn 2044-4761
dc.identifier.uri http://hdl.handle.net/10468/2923
dc.identifier.doi 10.1039/c3cy00194f
dc.description.abstract Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination. en
dc.description.sponsorship Higher Education Authority and Science Foundation Ireland (Irish Centre for High End Computing); European Commission (European Union FP7 Research Infrastructures Program PRACE, through the DECI-8 program, 10 contracts RI-261557 and RI-283493; European Union, COST Action CM1104 “Reducible Oxide Chemistry, Structure and Functions”) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Royal Society of Chemistry en
dc.rights © The Royal Society of Chemistry 2013. This is the Accepted Manuscript version of a published work that appeared in final form in Catalysis Science & Technology, http://dx.doi.org/10.1039/C3CY00194F en
dc.subject Density functional theory en
dc.subject Doped-TiO2 en
dc.subject Titanium(IV) Dioxide en
dc.subject Electronic structure en
dc.subject Transition metal en
dc.subject Oxygen vacancies en
dc.subject Anatase TiO2 en
dc.subject Surface en
dc.subject Irradation en
dc.title Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Michael Nolan, Tyndall Theory Modelling & Design Centre, University College Cork, Cork, Ireland. +353-21-490-3000 Email: michael.nolan@tyndall.ie en
dc.internal.availability Full text available en
dc.date.updated 2014-04-08T12:39:13Z
dc.description.version Accepted Version en
dc.internal.rssid 243940269
dc.internal.wokid 000321571500016
dc.contributor.funder Higher Education Authority en
dc.contributor.funder Science Foundation Ireland en
dc.contributor.funder European Commission en
dc.contributor.funder Seventh Framework Programme
dc.contributor.funder Partnership for Advanced Computing in Europe AISBL
dc.description.status Peer reviewed en
dc.identifier.journaltitle Catalysis Science & Technology en
dc.internal.copyrightchecked Yes !!CORA!! Yes en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress michael.nolan@tyndall.ie en
dc.relation.project info:eu-repo/grantAgreement/SFI/SFI Starting Investigator Research Grant (SIRG)/09/SIRG/I1620/IE/EMOIN: Engineering Metal Oxide Interfaces For Renewable Energy Photocatalysis/

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