Oxygen chemistry of halogen-doped CeO2(111)

Matthew J. Wolf, Ernst D. Larsson, Kersti Hermansson

Research output: Contribution to journalArticlepeer-review

Abstract

We study substitutional fluorine, chlorine and bromine impurities at CeO2(111), and their effects on the oxygen chemistry of the surface, using density functional theory. We find that impurity formation results in a halide ion and one Ce3+ion for all three halogens, although the formation energy depends strongly on the identity of the halogen; however, once formed, all three halogens exhibit a similar propensity to form impurity-impurity pairs. Furthermore, while the effects of halogen impurities on oxygen vacancy formation are marginal, they are more significant for oxygen molecule adsorption, due to electron transfer from the Ce3+ion which results in an adsorbed superoxide molecule. We also consider the displacement of a halide ion on to the surface by half of an oxygen molecule, and find that the energy required to do so depends strongly not only on the identity of the halogen, but also on whether or not a second halogen impurity, with its associated Ce3+ion, is present; if it is, then the process is greatly facilitated. Overall, our results demonstrate the existence of a rich variety of ways in which the oxygen chemistry of CeO2(111) may be modified by the presence of halogen dopants.

Original languageEnglish
Pages (from-to)19375-19385
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number35
DOIs
Publication statusPublished - 2021 Sep 21

Bibliographical note

Funding Information:
We acknowledge financial support from the Swedish Research Council (Vetenskapsr?det) and from the Swedish strategic collaborative research programme in e-science, eSSENCE. The calculations described in this paper were performed using resources provided by the Swedish National Infrastructure for Computing (SNIC) at NSC. We thank Dr J. Kullgren for commenting on a draft of the paper.

Funding Information:
We acknowledge financial support from the Swedish Research Council (Vetenskapsrådet) and from the Swedish strategic collaborative research programme in e-science, eSSENCE. The calculations described in this paper were performed using resources provided by the Swedish National Infrastructure for Computing (SNIC) at NSC. We thank Dr J. Kullgren for commenting on a draft of the paper.

Publisher Copyright:
© the Owner Societies 2021.

Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.

Subject classification (UKÄ)

  • Materials Chemistry

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