Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

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dc.check.date2017-08-09
dc.check.infoAccess to this article is restricted until 12 months after publication by the request of the publisher.en
dc.contributor.authorCarey, John J.
dc.contributor.authorLegesse, Merid
dc.contributor.authorNolan, Michael
dc.contributor.funderEuropean Commissionen
dc.contributor.funderEuropean Cooperation in Science and Technologyen
dc.contributor.funderScience Foundation Irelanden
dc.date.accessioned2016-10-20T14:05:34Z
dc.date.available2016-10-20T14:05:34Z
dc.date.issued2016-09
dc.date.updated2016-10-20T13:29:57Z
dc.description.abstractThe different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.en
dc.description.sponsorshipScience Foundation Ireland (Irish Centre for High-end Computing (ICHEC)); European Cooperation in Science and Technology (COST ACTION CM1104 “Reducible oxides: structure and function”.)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationCAREY, J. J., LEGESSE, M. & NOLAN, M. 2016. Low Valence Cation Doping of Bulk Cr2O3: Charge Compensation and Oxygen Vacancy Formation. The Journal of Physical Chemistry C, 120 (34), 19160-19174. doi:10.1021/acs.jpcc.6b05575en
dc.identifier.doi10.1021/acs.jpcc.6b05575
dc.identifier.endpage19174en
dc.identifier.issn1932-7447
dc.identifier.issued34en
dc.identifier.journaltitleJournal of Physical Chemistry Cen
dc.identifier.startpage19160en
dc.identifier.urihttps://hdl.handle.net/10468/3201
dc.identifier.volume120en
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP1::NMP/604296/EU/Catalytic Partial Oxidation of Bio Gas and Reforming of Pyrolysis Oil (Bio Oil) for an Autothermal Synthesis Gas Production and Conversion into Fuels/BIOGO-FOR-PRODUCTIONen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::SGA-CSA/681463/EU/COST at a turning point: A unique framework for pan-European ST cooperation as clear demonstration of European values/H2020
dc.relation.urihttp://pubs.acs.org/doi/full/10.1021/acs.jpcc.6b05575
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/full/10.1021/acs.jpcc.6b05575en
dc.subjectGeneralized gradienten
dc.subjectApproximationen
dc.subjectDensity-functional theoryen
dc.subjectTotal-energy calculationsen
dc.subjectWave basis seten
dc.subjectElectrical-conductivityen
dc.subjectElectronic-structureen
dc.subjectMagnetic-propertiesen
dc.subjectSelf-diffusionen
dc.subjectAb initioen
dc.subjectDoped Cr2O3en
dc.titleLow valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formationen
dc.typeArticle (peer-reviewed)en
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