Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius
dc.contributor.author | Nolan, Michael | |
dc.contributor.funder | Higher Education Authority | en |
dc.contributor.funder | Science Foundation Ireland | en |
dc.date.accessioned | 2016-07-22T10:44:01Z | |
dc.date.available | 2016-07-22T10:44:01Z | |
dc.date.issued | 2011-03-10 | |
dc.date.updated | 2013-10-29T22:03:38Z | |
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.description.status | Peer reviewed | en |
dc.description.version | Accepted Version | en |
dc.format.mimetype | application/pdf | en |
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. http://dx.doi.org/10.1021/jp112112u | en |
dc.identifier.doi | 10.1021/jp112112u | |
dc.identifier.endpage | 6681 | en |
dc.identifier.issn | 1932-7447 | |
dc.identifier.issn | 1932-7455 | |
dc.identifier.issued | 14 | en |
dc.identifier.journaltitle | Journal of Physical Chemistry C | en |
dc.identifier.startpage | 6671 | en |
dc.identifier.uri | https://hdl.handle.net/10468/2927 | |
dc.identifier.volume | 115 | 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 http://pubs.acs.org/doi/abs/10.1021/jp112112u | 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 |
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