Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO2(111)

Sutton, Jonathan E.; Beste, Ariana

doi:10.1103/PhysRevB.92.144105

Title: Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO₂(111)

Journal Article · Mon Oct 12 00:00:00 EDT 2015 · Physical Review B

DOI:https://doi.org/10.1103/PhysRevB.92.144105· OSTI ID:1286875

Sutton, Jonathan E. ^[1]; Beste, Ariana ^[2]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division

In this study, we use density functional theory to explain the preferred structure of partially reduced CeO₂(111). Low-energy ordered structures are formed when the vacancies are isolated (maximized intervacancy separation) and the size of the Ce³⁺ ions is minimized. Both conditions help minimize disruptions to the lattice around the vacancy. The stability of the ordered structures suggests that isolated vacancies are adequate for modeling more complex (e.g., catalytic) systems. Oxygen diffusion barriers are predicted to be low enough that O diffusion between vacancies is thermodynamically controlled at room temperature. The O-diffusion-reaction energies and barriers are decreased when one Ce f electron hops from a nearest-neighbor Ce cation to a next-nearest-neighbor Ce cation, with a barrier that has been estimated to be slightly less than the barrier to O diffusion in the absence of polaron hopping. In conculsion, this indicates that polaron hopping plays a key role in facilitating the overall O diffusion process, and depending on the relative magnitudes of the polaron hopping and O diffusion barriers, polaron hopping may be the kinetically limiting process.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1286875

Alternate ID(s):: OSTI ID: 1224645

Journal Information:: Physical Review B, Vol. 92, Issue 14; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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Photon-Induced Spintronic Polaron Channel Modulator of CeO _2- _x NP Thin Films Hydrogen Evolution Cells Lai, Yi-Sheng; Su, Yen-Hsun Advanced Electronic Materials, Vol. 5, Issue 1 https://doi.org/10.1002/aelm.201800570	journal	November 2018

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Title: Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO2(111)

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Title: Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO₂(111)