Metal oxide nanocluster-modified TiO2 as solar activated photocatalyst materials

dc.contributor.authorFronzi, Marco
dc.contributor.authorIwaszuk, Anna
dc.contributor.authorLucid, Aoife K.
dc.contributor.authorNolan, Michael
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderEuropean Cooperation in Science and Technologyen
dc.contributor.funderEuropean Commissionen
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderPartnership for Advanced Computing in Europe AISBLen
dc.description.abstractIn this review we describe our work on new TiO2 based photocatalysts. The key concept in our work is to form new composite structures by the modification of rutile and anatase TiO2 with nanoclusters of metal oxides and our density functional theory (DFT) level simulations are validated by experimental work synthesizing and characterizing surface-modified TiO2. We use DFT to show that nanoclusters of different metal oxides, TiO2, SnO/SnO2, PbO/PbO2, NiO and CuO can be adsorbed at rutile and anatase surfaces and can induce red shifts in the absorption edge to enable visible light absorption which is the first key requirement for a practical photocatalyst. We furthermore determine the origin of the red shift and discuss the factors influencing this shift and the fate of excited electrons and holes. For p-block metal oxides we show how the oxidation state of Sn and Pb can be used to tune both the magnitude of the red shift and also its mechanism. Finally, aiming to make our models more realistic, we present some new results on the stability of water at rutile and anatase surfaces and the effect of water on oxygen vacancy formation and on nanocluster modification. These nanocluster-modified TiO2 structures form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with the suitable choice of nanocluster modifier can be applied to CO2 reduction.en
dc.description.sponsorshipEuropean Commission (European Commission through the COST Action CM1104 “Reducible Metal Oxides, Structure and Function”); Partnership for Advanced Computing in Europe AISBL, (PRACE (RI-261557, RI-283493 and RI-312763) (Distributed European Computing Initiative (DECI)); Science Foundation Ireland and Higher Education Authority (Irish Centre for High End Computing)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.identifier.citationMarco, F., Anna, I., Aoife, L. and Michael, N. (2016) 'Metal oxide nanocluster-modified TiO 2 as solar activated photocatalyst materials', Journal of Physics: Condensed Matter, 28(7), 074006 (23pp). doi: 10.1088/0953-8984/28/7/074006en
dc.identifier.journaltitleJournal of Physics-Condensed Matteren
dc.publisherIOP Publishingen
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/en
dc.relation.projectinfo: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.rights© 2016 IOP Publishing Ltd. This is an author-created, un-copyedited version of an article accepted for publication in Journal of Physics: Condensed Matter. The publisher is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at
dc.subjectDensity functional theoryen
dc.subjectSurface modificationen
dc.subjectMetal oxides,en
dc.subjectBand gapen
dc.subjectVisible-light photocatalysisen
dc.subjectCharge-carrier separationen
dc.subjectModified titanium-dioxideen
dc.subjectN-doped TiO2en
dc.subjectRutile TiO2en
dc.subjectAnatase TiO2en
dc.subject110 surfacesen
dc.subjectIron oxideen
dc.subjectLone pairen
dc.titleMetal oxide nanocluster-modified TiO2 as solar activated photocatalyst materialsen
dc.typeArticle (peer-reviewed)en
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