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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 (P4 2/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 O 2- 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.

Authors:
 [1];  [2];  [1];  [3]; ORCiD logo [4]; ORCiD logo [5];  [6];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [1]
  1. Univ. of Science and Technology Beijing (China). Beijing Advanced Innovation Center for Materials Genome Engineering. Dept. of Physical Chemistry. State Key Lab. for Advanced Metals and Materials
  2. Beijing Inst. of Technology (China). School of Aerospace Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  5. Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics
  6. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Science and Technology Beijing (China); Beijing Inst. of Technology (China); Chinese Academy of Sciences (CAS), Beijing (China)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NNSFC); Program for Changjiang Scholars (China); Innovative Research Team in University (China); Program of Introducing Talents of Discipline to Universities (China); Thousand Young Talents Program of China
OSTI Identifier:
1505144
Grant/Contract Number:  
AC02-06CH11357; 21590793; 21731001; 11572040; IRT1207; B14003; U1501501
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electron transfer; structural properties

Citation Formats

Zhu, He, Yang, Chao, Li, Qiang, Ren, Yang, Neuefeind, Joerg C., Gu, Lin, Liu, Huibiao, Fan, Longlong, Chen, Jun, Deng, Jinxia, Wang, Na, Hong, Jiawang, and Xing, Xianran. Charge transfer drives anomalous phase transition in ceria. United States: N. p., 2018. Web. doi:10.1038/s41467-018-07526-x.
Zhu, He, Yang, Chao, Li, Qiang, Ren, Yang, Neuefeind, Joerg C., Gu, Lin, Liu, Huibiao, Fan, Longlong, Chen, Jun, Deng, Jinxia, Wang, Na, Hong, Jiawang, & Xing, Xianran. Charge transfer drives anomalous phase transition in ceria. United States. doi:10.1038/s41467-018-07526-x.
Zhu, He, Yang, Chao, Li, Qiang, Ren, Yang, Neuefeind, Joerg C., Gu, Lin, Liu, Huibiao, Fan, Longlong, Chen, Jun, Deng, Jinxia, Wang, Na, Hong, Jiawang, and Xing, Xianran. Thu . "Charge transfer drives anomalous phase transition in ceria". United States. doi:10.1038/s41467-018-07526-x. https://www.osti.gov/servlets/purl/1505144.
@article{osti_1505144,
title = {Charge transfer drives anomalous phase transition in ceria},
author = {Zhu, He and Yang, Chao and Li, Qiang and Ren, Yang and Neuefeind, Joerg C. and Gu, Lin and Liu, Huibiao and Fan, Longlong and Chen, Jun and Deng, Jinxia and Wang, Na and Hong, Jiawang and Xing, Xianran},
abstractNote = {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.},
doi = {10.1038/s41467-018-07526-x},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {2018},
month = {11}
}

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Figures / Tables:

Fig. 1 Fig. 1: Phase transition-induced anomalous thermal expansion in nanosized ceria. a Temperature dependence of the lattice parameters extracting from Xray diffraction Rietveld refinements for the CeO2 in different sizes. The inset depicts the unit cell of CeO2 with the space group Fm-3m. The errors are much smaller than the sizemore » of data symbols in the figure. The blue area emphasizes the temperature range of thermal expansion abnormity. b Comparison of the (1 1 1) diffraction peaks of 5 nm ceria data at different temperatures. The solid line depicts trend of the peak positions as the temperature changes. The blue area shows the temperature range of the negative thermal expansion. c Specific heat capacity of the 5 nm ceria measured from −150 °C to 150 °C. The red line in the inset is the heat capacity peak in the transition region excluding the fitted background (i.e., (Cp–Cfit)), and the green line shows the estimated entropy obtained by integrating (Cp–Cfit)/T. The blue area corresponds to the blue area in Fig. 1a. d The annular bright-field (ABF) image with a common tilt axis of [0 0 1] for 5 nm ceria. The scale bar is 1 nm. The inset shows the corresponding ABF in line profile acquired along the oxygen-atom columns (pink line in the figure). The arrow shows the oxygen vacancy site marked with hollow block« less

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