Charge transfer drives anomalous phase transition in ceria

He Zhu; Chao Yang; Qiang Li; Yang Ren; Joerg C. Neuefeind; Lin Gu; Huibiao Liu; Longlong Fan; Jun Chen; Jinxia Deng; Na Wang; Jiawang Hong; Xianran Xing

doi:10.1038/s41467-018-07526-x

Charge transfer drives anomalous phase transition in ceria

He Zhu, Chao Yang, Qiang Li, Yang Ren, Joerg C. Neuefeind, Lin Gu, Huibiao Liu, Longlong Fan, Jun Chen, Jinxia Deng, Na Wang, Jiawang Hong, Xianran Xing^*

^*Corresponding author for this work

School of Aerospace Engineering

Research output: Contribution to journal › Article › peer-review

53 Citations (Scopus)

Abstract

Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P4₂/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of −25 °C–75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O²⁻ anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.

Original language	English
Article number	5063
Journal	Nature Communications
Volume	9
Issue number	1
DOIs	https://doi.org/10.1038/s41467-018-07526-x
Publication status	Published - 1 Dec 2018

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title = "Charge transfer drives anomalous phase transition in ceria",

abstract = "Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P42/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of −25 °C–75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O2− anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.",

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T1 - Charge transfer drives anomalous phase transition in ceria

AU - Zhu, He

AU - Yang, Chao

AU - Li, Qiang

AU - Ren, Yang

AU - Neuefeind, Joerg C.

AU - Gu, Lin

AU - Liu, Huibiao

AU - Fan, Longlong

AU - Chen, Jun

AU - Deng, Jinxia

AU - Wang, Na

AU - Hong, Jiawang

AU - Xing, Xianran

PY - 2018/12/1

Y1 - 2018/12/1

N2 - Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P42/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of −25 °C–75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O2− anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.

AB - Ceria has conventionally been thought to have a cubic fluorite structure with stable geometric and electronic properties over a wide temperature range. Here we report a reversible tetragonal (P42/nmc) to cubic (Fm-3m) phase transition in nanosized ceria, which triggers negative thermal expansion in the temperature range of −25 °C–75 °C. Local structure investigations using neutron pair distribution function and Raman scatterings reveal that the tetragonal phase involves a continuous displacement of O2− anions along the fourfold axis, while the first-principles calculations clearly show oxygen vacancies play a pivotal role in stabilizing the tetragonal ceria. Further experiments provide evidence of a charge transfer between oxygen vacancies and 4f orbitals in ceria, which is inferred to be the mechanism behind this anomalous phase transition.

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Charge transfer drives anomalous phase transition in ceria

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