Influence of trivalent doping on point and Frenkel defect formation in bulk chromium (III) oxide

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dc.check.date2019-05-02
dc.check.infoAccess to this article is restricted for 24 months after publication by request of the publisher.en
dc.contributor.authorCarey, John J.
dc.contributor.authorNolan, Michael
dc.contributor.funderEuropean Commissionen
dc.contributor.funderSeventh Framework Programmeen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderEuropean Cooperation in Science and Technologyen
dc.contributor.funderHigher Education Authorityen
dc.date.accessioned2017-11-02T12:46:00Z
dc.date.available2017-11-02T12:46:00Z
dc.date.issued2017-05-02
dc.date.updated2017-11-02T12:36:44Z
dc.description.abstractSubstitutional doping in metal oxides is a well-known approach to modifying properties such as ionic conductivity or activity in catalysis. Chromium (III) oxide is an attractive reducible material that has potential use as an oxygenation catalyst, and the fact that it maintains its integrity at high operating temperatures makes it useful for high temperature methanol synthesis and solid oxide fuel cells. Understanding the defect chemistry of Cr2O3 is important for rational catalyst design, in particular when the material is modified by isovalent doping. Density functional theory calculations with a Hubbard +U correction applied to the Cr 3d and O 2p states are used to investigate isovalent doping with Al3+, Fe3+ and La3+ cations. Point defects including Cr and O vacancies, and Frenkel defects are investigated and the effect of cation doping on the defect formation energies in Cr2O3 is explored. Our calculations show that Cr Frenkel and peroxide point defects are the most favourable defects in undoped Cr2O3. Al3+ doping in Cr2O3 does not change the defect formation energies over undoped Cr2O3, and Fe3+ doping improves oxygen vacancy formation while greatly increasing the formation energies of other defects that are potential competing processes that may kill ionic conductivity. La3+ doping in Cr2O3 is found to also improve oxygen vacancy formation and induces a considerable decrease in the cost to form Cr vacancies and Frenkel defects. The modifications to the defect formation energies induced by these dopants in Cr2O3 can be used to impede formation of undesirable defects, thus enhancing ionic conductivity for oxygenation catalysis.en
dc.description.sponsorshipScience Foundation Ireland and Higher Education Authority (SFI/HEA funded Irish Centre for High-end Computing (ICHEC) and SFI funded local clusters at Tyndall); European Commission (European Cooperation in Science and Technology COST Action CM1104 “Reducible Metal Oxides, Structure and Function”)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationCarey, J. J. and Nolan, M. (2017) 'Influence of trivalent doping on point and Frenkel defect formation in bulk chromium (III) oxide', Solid State Ionics, 307(Supplement C), pp. 51-64. doi: 10.1016/j.ssi.2017.04.016en
dc.identifier.doi10.1016/j.ssi.2017.04.016
dc.identifier.endpage64en
dc.identifier.issn0167-2738
dc.identifier.issuedSupplement Cen
dc.identifier.journaltitleSolid State Ionicsen
dc.identifier.startpage51en
dc.identifier.urihttps://hdl.handle.net/10468/4949
dc.identifier.volume307en
dc.language.isoenen
dc.publisherElsevieren
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.urihttp://www.sciencedirect.com/science/article/pii/S0167273817302072
dc.rights© 2017 Published by Elsevier B.V. This manuscript version is made available under the CC BY-NC-ND 4.0 license.en
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectIsovalent dopingen
dc.subjectDensity functional theoryen
dc.subjectCatalysisen
dc.subjectSOFCen
dc.subjectMetal oxideen
dc.titleInfluence of trivalent doping on point and Frenkel defect formation in bulk chromium (III) oxideen
dc.typeArticle (peer-reviewed)en
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