Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

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dc.contributor.authorJin, Qiliang
dc.contributor.authorFujishima, Musashi
dc.contributor.authorIwaszuk, Anna
dc.contributor.authorNolan, Michael
dc.contributor.authorTada, Hiroaki
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderEuropean Commissionen
dc.contributor.funderMinistry of Education, Culture, Sports, Science and Technologyen
dc.contributor.funderNippon Sheet Glass Foundation for Materials Science and Engineeringen
dc.contributor.funderSumitomo Foundationen
dc.contributor.funderEuropean Cooperation in Science and Technology
dc.date.accessioned2016-07-22T09:32:01Z
dc.date.available2016-07-22T09:32:01Z
dc.date.issued2013-10-16
dc.date.updated2014-04-08T12:42:43Z
dc.description.abstractCu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.en
dc.description.sponsorshipMinistry of Education, Science, Sport, and Culture, Japan (Grant-in-Aid for Scientific Research (C) No. 24550239); Nippon Sheet Glass Foundation, Japan (Materials Science and Engineering); Sumitomo Foundation, Japan; Science Foundation Ireland and Higher Education Authority (Irish Centre for High End Computing); European Commission (COST Action CM1104 “Reducible Metal Oxides, Structure and Function”), (Partnership in Advanced Computing (PRACE), contracts RI-261557, RI-283493 and RI-312763), (DECI-9 initiative: access to the JUROPA Computer at Forschungszentrum Juelich)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationJin, Q., Fujishima, M., Iwaszuk, A., Nolan, M. and Tada, H (2013) 'Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities', Journal of Physical Chemistry C, 117(45), pp. 23848-23857. http://pubs.acs.org/doi/abs/10.1021/jp4085525en
dc.identifier.doi10.1021/jp4085525
dc.identifier.endpage23857en
dc.identifier.issn1932-7447
dc.identifier.issn1932-7455
dc.identifier.issued45en
dc.identifier.journaltitleJournal of Physical Chemistry Cen
dc.identifier.startpage23848en
dc.identifier.urihttps://hdl.handle.net/10468/2925
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.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in 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/jp4085525en
dc.subjectPhotocatalytic reactionen
dc.subjectTiO2 photocatalystsen
dc.subjectOxygen vacanciesen
dc.subjectTransition metalen
dc.subjectIron oxideen
dc.subjectIrradationen
dc.subjectDioxideen
dc.subjectSemiconductoren
dc.subjectDepositionen
dc.subjectParticlesen
dc.titleLoading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activitiesen
dc.typeArticle (peer-reviewed)en
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