Origin of the visible-light response of nickel(II) oxide cluster surface modified titanium(IV) dioxide

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dc.contributor.author Iwaszuk, Anna
dc.contributor.author Nolan, Michael
dc.contributor.author Jin, Qiliang
dc.contributor.author Fujishima, Musashi
dc.contributor.author Tada, Hiroaki
dc.date.accessioned 2014-07-22T13:02:35Z
dc.date.available 2014-07-22T13:02:35Z
dc.date.issued 2013-01-24
dc.identifier.citation Iwaszuk, A., Nolan, M., Jin, Q., Fujishima, M. and Tada, H. (2013) 'Origin of the Visible-Light Response of Nickel(II) Oxide Cluster Surface Modified Titanium(IV) Dioxide', The Journal of Physical Chemistry C, 117(6), pp. 2709-2718. doi: 10.1021/jp306793r en
dc.identifier.volume 117 en
dc.identifier.issued 6 en
dc.identifier.startpage 2709 en
dc.identifier.endpage 2718 en
dc.identifier.issn 1932-7447
dc.identifier.uri http://hdl.handle.net/10468/1595
dc.identifier.doi 10.1021/jp306793r
dc.description.abstract A number of NiO clusters have been formed on TiO2 (anatase/rutile = 4/1 w/w, P-25, Degussa) in a highly dispersed state (NiO/TiO2) by the chemisorption-calcination cycle technique. The NiO/TiO2 causes high visible-light activities for the degradations of 2-naphthol and p-cresol exceeding those of FeOx/TiO2 (Tada et al. Angew. Chem., Int. Ed. 2011, 50, 3501-3505). The main purpose of this study is to clarify the origin at an electronic level by the density functional simulation for NiO, Ni2O2, Ni3O3, and Ni4O4 clusters supported on TiO2 rutile (110) and anatase (001) surfaces. The clusters adsorb strongly on both rutile and anatase with adsorption energies ranging from -3.18 to -6.15 eV, creating new interfacial bonds between the clusters and both surfaces. On rutile, intermetallic Ni-Ti bonds facilitate stronger binding compared with anatase. The electronic structure shows that the top of the valence bands (VBs) of rutile and anatase arises from electronic states on the NiO cluster. On the other hand, the conduction band of rutile is from the Ti 3d states, whereas NiO cluster levels are generated near the conduction band minimum of anatase. This is in contrast to the SnO2/rutile TiO2 system, where the density of states near the conduction band minimum increases with the VB unmodified. In the NiO/TiO2 system, the band gaps of both rutile and anatase are narrowed by up to 0.8 eV compared with pristine TiO2, which pushes the photoactivity into the visible region. In view of the calculated electronic structure, we have attributed the enhanced photocataltyic activity both to the charge separation due to the excitation from the Ni 3d surface sub-band to the TiO2 conduction band and the action of the NiO species as a mediator for the electron transfer from the TiO2 conduction band to O-2. en
dc.description.sponsorship Higher Education Authority (Irish Centre for High End Computing); European Commission (COST Action CM1104 Reducible Oxide Chemistry, Structure and Functions); Ministry of Education, Science, Sport, and Culture, Japan (Grant-in-Aid for Scientific Research (C) no. 24550239) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher American Chemical Society en
dc.relation.uri http://pubs.acs.org/doi/abs/10.1021/jp306793r
dc.rights © 2013 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jp306793r en
dc.subject Carbon-doped TiO2 en
dc.subject Anatase TiO2 en
dc.subject Photocatalytic materials en
dc.subject Electronic structures en
dc.subject Organic compounds en
dc.subject Oxygen vacancies en
dc.subject Transition metal en
dc.subject 1st principles en
dc.subject Semiconductor en
dc.subject Irradiation en
dc.title Origin of the visible-light response of nickel(II) oxide cluster surface modified titanium(IV) dioxide 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 2013-10-29T21:27:06Z
dc.description.version Accepted Version en
dc.internal.rssid 206307501
dc.internal.wokid 000315181800039
dc.contributor.funder Higher Education Authority en
dc.contributor.funder European Commission
dc.contributor.funder Ministry of Education, Culture, Sports, Science and Technology
dc.contributor.funder Nippon Sheet Glass Foundation for Materials Science and Engineering
dc.contributor.funder Sumitomo Foundation
dc.contributor.funder Science Foundation Ireland
dc.contributor.funder European Cooperation in Science and Technology
dc.description.status Peer reviewed en
dc.identifier.journaltitle Journal of Physical Chemistry C en
dc.internal.copyrightchecked Yes !!CORA!! AV permitted if mandated by funder. 12 month embargo. en
dc.internal.licenseacceptance Yes 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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