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

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dc.contributor.authorIwaszuk, Anna
dc.contributor.authorNolan, Michael
dc.contributor.authorJin, Qiliang
dc.contributor.authorFujishima, Musashi
dc.contributor.authorTada, Hiroaki
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderEuropean Commission
dc.contributor.funderMinistry of Education, Culture, Sports, Science and Technology
dc.contributor.funderNippon Sheet Glass Foundation for Materials Science and Engineering
dc.contributor.funderSumitomo Foundation
dc.contributor.funderScience Foundation Ireland
dc.contributor.funderEuropean Cooperation in Science and Technology
dc.date.accessioned2014-07-22T13:02:35Z
dc.date.available2014-07-22T13:02:35Z
dc.date.issued2013-01-24
dc.date.updated2013-10-29T21:27:06Z
dc.description.abstractA 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.sponsorshipHigher 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.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationIwaszuk, 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/jp306793ren
dc.identifier.doi10.1021/jp306793r
dc.identifier.endpage2718en
dc.identifier.issn1932-7447
dc.identifier.issued6en
dc.identifier.journaltitleJournal of Physical Chemistry Cen
dc.identifier.startpage2709en
dc.identifier.urihttps://hdl.handle.net/10468/1595
dc.identifier.volume117en
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
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.relation.urihttp://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/jp306793ren
dc.subjectCarbon-doped TiO2en
dc.subjectAnatase TiO2en
dc.subjectPhotocatalytic materialsen
dc.subjectElectronic structuresen
dc.subjectOrganic compoundsen
dc.subjectOxygen vacanciesen
dc.subjectTransition metalen
dc.subject1st principlesen
dc.subjectSemiconductoren
dc.subjectIrradiationen
dc.titleOrigin of the visible-light response of nickel(II) oxide cluster surface modified titanium(IV) dioxideen
dc.typeArticle (peer-reviewed)en
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