Reactivity of sub 1 nm supported clusters: (TiO2)(n) clusters supported on rutile TiO2 (110)

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dc.contributor.authorIwaszuk, Anna
dc.contributor.authorNolan, Michael
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderScience Foundation Irelanden
dc.date.accessioned2014-09-18T12:28:18Z
dc.date.available2014-09-18T12:28:18Z
dc.date.issued2011-02-18
dc.date.updated2013-10-29T22:26:27Z
dc.description.abstractMetal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO2 clusters, Ti2O4, Ti3O6 and Ti4O8 supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO2, demonstrating the usefulness of this composite system for redox catalysis.en
dc.description.sponsorshipHigher Education Authority and Science Foundation Ireland (Irish Centre for High End Computing)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationIwaszuk, A. and Nolan, M. (2011) 'Reactivity of sub 1 nm supported clusters: (TiO2)n clusters supported on rutile TiO2 (110)', Physical Chemistry Chemical Physics, 13(11), pp. 4963-4973. doi: 10.1039/C0CP02030Cen
dc.identifier.doi10.1039/C0CP02030C
dc.identifier.endpage4973en
dc.identifier.issn1463-9076
dc.identifier.issued11en
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen
dc.identifier.startpage4963en
dc.identifier.urihttps://hdl.handle.net/10468/1668
dc.identifier.volume13en
dc.language.isoenen
dc.publisherThe Royal Society of Chemistryen
dc.rights© The Royal Society of Chemistry 2011. This is the Accepted Manuscript version of a published work that appeared in final form in Physical Chemistry Chemical Physics. To access the final published version of record, see http://pubs.rsc.org/en/content/articlepdf/2011/cp/c0cp02030cen
dc.subjectDensity functional theory (DFT)en
dc.subjectVisible-light photocatalysisen
dc.subjectVanadium-oxide catalystsen
dc.subjectMixed-metal oxideen
dc.subjectOxygen vacanciesen
dc.subjectMonolayer catalystsen
dc.subjectSurface-structureen
dc.subjectNanometer levelen
dc.subjectNanoparticlesen
dc.subjectNanometer levelen
dc.subjectCo-oxidationen
dc.titleReactivity of sub 1 nm supported clusters: (TiO2)(n) clusters supported on rutile TiO2 (110)en
dc.typeArticle (peer-reviewed)en
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