skip to main content

DOE PAGESDOE PAGES

Title: Charge transfer drives anomalous phase transition in ceria

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:
Grant/Contract Number:
AC02-06CH11357; 21590793; 21731001; 11572040; IRT1207; B14003; U1501501
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
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
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electron transfer; structural properties
OSTI Identifier:
1505144

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., 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. 2018. "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}
}

Works referenced in this record:

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996