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

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dc.contributor.author Carey, John J.
dc.contributor.author Legesse, Merid
dc.contributor.author Nolan, Michael
dc.date.accessioned 2016-10-20T14:05:34Z
dc.date.available 2016-10-20T14:05:34Z
dc.date.issued 2016-09
dc.identifier.citation CAREY, 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.6b05575 en
dc.identifier.volume 120 en
dc.identifier.issued 34 en
dc.identifier.startpage 19160 en
dc.identifier.endpage 19174 en
dc.identifier.issn 1932-7447
dc.identifier.uri http://hdl.handle.net/10468/3201
dc.identifier.doi 10.1021/acs.jpcc.6b05575
dc.description.abstract The 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.sponsorship Science 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.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher American Chemical Society en
dc.relation.uri http://pubs.acs.org/doi/full/10.1021/acs.jpcc.6b05575
dc.rights This 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.6b05575 en
dc.subject Generalized gradient en
dc.subject Approximation en
dc.subject Density-functional theory en
dc.subject Total-energy calculations en
dc.subject Wave basis set en
dc.subject Electrical-conductivity en
dc.subject Electronic-structure en
dc.subject Magnetic-properties en
dc.subject Self-diffusion en
dc.subject Ab initio en
dc.subject Doped Cr2O3 en
dc.title Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation 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.check.info Access to this article is restricted until 12 months after publication by the request of the publisher. en
dc.check.date 2017-08-09
dc.date.updated 2016-10-20T13:29:57Z
dc.description.version Accepted Version en
dc.internal.rssid 368650447
dc.internal.wokid WOS:000382596900025
dc.contributor.funder European Commission en
dc.contributor.funder European Cooperation in Science and Technology en
dc.contributor.funder Science Foundation Ireland en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Journal of Physical Chemistry C en
dc.internal.copyrightchecked No en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress michael.nolan@tyndall.ie en
dc.relation.project info: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-PRODUCTION en
dc.relation.project info: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

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