Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

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Show simple item record Nolan, Michael 2016-07-22T10:44:01Z 2016-07-22T10:44:01Z 2011-03-10
dc.identifier.citation Nolan, M. (2011) 'Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius', Journal of Physical Chemistry C, 115(14), pp. 6671-6681. en
dc.identifier.volume 115 en
dc.identifier.issued 14 en
dc.identifier.startpage 6671 en
dc.identifier.endpage 6681 en
dc.identifier.issn 1932-7447
dc.identifier.issn 1932-7455
dc.identifier.doi 10.1021/jp112112u
dc.description.abstract In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome. en
dc.description.sponsorship Science Foundation Ireland (Starting Investigator Research Grant Program (EMOIN (SIRG/09/I1620)); Science Foundation Ireland and Higher Education Authority (Irish Centre for High End Computing (ICHEC)) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher American Chemical Society en
dc.rights © 2011 American Chemical Society. 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 en
dc.subject Density functional theory en
dc.subject Transform infra-red spectroscopy en
dc.subject Oxygen vacancy formation en
dc.subject Augmented wave method en
dc.subject Ceria surfaces en
dc.subject Electronic structure en
dc.subject Carbon monoxide en
dc.subject Co-adsorption en
dc.subject Stabilised zirconia en
dc.subject Low-index surfaces en
dc.title Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius 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: en
dc.internal.availability Full text available en 2013-10-29T22:03:38Z
dc.description.version Accepted Version en
dc.internal.rssid 90194286
dc.internal.wokid 000289215400066
dc.contributor.funder Higher Education Authority 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 Yes. !!CORA!! en
dc.internal.licenseacceptance Yes en

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