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

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dc.contributor.author Iwaszuk, Anna
dc.contributor.author Nolan, Michael
dc.date.accessioned 2014-09-18T12:28:18Z
dc.date.available 2014-09-18T12:28:18Z
dc.date.issued 2011-02-18
dc.identifier.citation Iwaszuk, 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/C0CP02030C en
dc.identifier.volume 13 en
dc.identifier.issued 11 en
dc.identifier.startpage 4963 en
dc.identifier.endpage 4973 en
dc.identifier.issn 1463-9076
dc.identifier.uri http://hdl.handle.net/10468/1668
dc.identifier.doi 10.1039/C0CP02030C
dc.description.abstract Metal 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.sponsorship Higher Education Authority and Science Foundation Ireland (Irish Centre for High End Computing) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher The Royal Society of Chemistry en
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/c0cp02030c en
dc.subject Density functional theory (DFT) en
dc.subject Visible-light photocatalysis en
dc.subject Vanadium-oxide catalysts en
dc.subject Mixed-metal oxide en
dc.subject Oxygen vacancies en
dc.subject Monolayer catalysts en
dc.subject Surface-structure en
dc.subject Nanometer level en
dc.subject Nanoparticles en
dc.subject Nanometer level en
dc.subject Co-oxidation en
dc.title Reactivity of sub 1 nm supported clusters: (TiO2)(n) clusters supported on rutile TiO2 (110) 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 2013-10-29T22:26:27Z
dc.description.version Accepted Version en
dc.internal.rssid 90194394
dc.internal.wokid 000287930100025
dc.contributor.funder Higher Education Authority en
dc.contributor.funder Science Foundation Ireland en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Physical Chemistry Chemical Physics en
dc.internal.copyrightchecked Yes. !! CORA - AV required, set statement and 12 month embargo!! en
dc.internal.licenseacceptance Yes en


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