TiO2 nanocluster modified-rutile TiO2 photocatalyst: a first principles investigation

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dc.contributor.authorIwaszuk, Anna
dc.contributor.authorMulheran, Paul A.
dc.contributor.authorNolan, Michael
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderEuropean Commission
dc.contributor.funderEuropean Cooperation in Science and Technology
dc.contributor.funderEngineering and Physical Sciences Research Council
dc.date.accessioned2014-07-22T11:47:58Z
dc.date.available2014-07-22T11:47:58Z
dc.date.issued2013-01-02
dc.date.updated2013-05-10T10:28:33Z
dc.description.abstractTitanium dioxide is an important photocatalytic material with much activity in modifying it to achieve visible light absorption. Recently, studies targeting the modification of TiO2 with metal oxide nano clusters have investigated heterostructures which show potential as new TiO2-based photocatalytic materials with visible light absorption and improved photocatalytic activity. Obtaining detailed insights into the influence of surface modification on the photocatalytic properties of TiO2 will further the possibilities for using this approach to develop new photocatalysts. In this paper, we present the results of density functional theory (DFT) simulations of the TiO2 rutile (110) surface modified with TiO2 nanoclusters ((TiO2)(n): Ti5O10, Ti6O12, Ti8O16, Ti16O32, Ti30O60), with diameters up to 1.5 nm, which is a cluster size achievable in experiments. The clusters adsorb strongly at the surface giving adsorption energies from -2.7 eV to -6.7 eV. The resulting structures show a large number of new Ti-O bonds created between the cluster and the surface, so that the new bonds enhance the stability. The electronic density of states (EDOS) shows that the valence band edge is shifted upwards, due to new nanocluster derived states in this region, while the conduction band is unchanged and composed of the Ti 3d states from the surface. This reduces the band gap over bare TiO2, potentially shifting light absorption into the visible region. The valence and conduction band composition of these heterostructures will favour spatial separation of electrons and holes after light excitation, thus giving improved photocatalytic properties in these novel structures.en
dc.description.sponsorshipScience Foundation Ireland and Higher Education Authority (SFI and Higher Education Authority funded Irish Centre for High End Computing); European Commission (European Cooperation in Science and Technology COST Action CM1104 “Reducible Oxide Chemistry, Structure and Functions”); Engineering and Physical Sciences Research Council (EPSRC grant EP/C524349)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationIwaszuk, A., Mulheran, P. A. and Nolan, M. (2013) 'TiO2 nanocluster modified-rutile TiO2 photocatalyst: a first principles investigation', Journal of Materials Chemistry A, 1(7), pp. 2515-2525. doi: 10.1039/c2ta01582jen
dc.identifier.doi10.1039/c2ta01582j
dc.identifier.endpage2525en
dc.identifier.issn2050-7488
dc.identifier.issued7en
dc.identifier.journaltitleJournal of Materials Chemistry Aen
dc.identifier.startpage2515en
dc.identifier.urihttps://hdl.handle.net/10468/1594
dc.identifier.volume1en
dc.language.isoenen
dc.publisherThe Royal Society of Chemistryen
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI Starting Investigator Research Grant (SIRG)/09/SIRG/I1620/IE/EMOIN: Engineering Metal Oxide Interfaces For Renewable Energy Photocatalysis/
dc.rights© The Royal Society of Chemistry 2013. This is the Accepted Manuscript version of a published work that appeared in final form in Journal of Materials Chemistry A. To access the final published version of record, see http://pubs.rsc.org/en/content/articlepdf/2013/ta/c2ta01582jen
dc.subjectVisible-light photocatalysisen
dc.subjectDensity-functional theoryen
dc.subjectSolid-solid interfaceen
dc.subjectAnatase TiO2en
dc.subjectDoped TiO2en
dc.subjectTitanium(IV) dioxideen
dc.subjectElectronic structureen
dc.subjectSurface modificationen
dc.subjectCharge separationen
dc.subjectOxygen vacanciesen
dc.titleTiO2 nanocluster modified-rutile TiO2 photocatalyst: a first principles investigationen
dc.typeArticle (peer-reviewed)en
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