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Potential Control of Oxygen Non-Stoichiometry in Cerium Oxide and Phase Transition Away from Equilibrium

  • Catherine Dejoie
    Catherine Dejoie
    European Synchrotron Radiation Facility, 71 Avenue des Martyrs, CS 40220, Grenoble Cedex 9 38043, France
    Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  • Yi Yu
    Yi Yu
    School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
    Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States
    More by Yi Yu
  • Fabiano Bernardi
    Fabiano Bernardi
    Programa de Pós-Graduação em Física, Instituto de Física, Universidade Federal do Rio Grande do Sul (UFRGS), Av. Bento Gonçalves, 9500, Porto Alegre 91501-970, Rio Grande do Sul, Brazil
    Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  • Nobumichi Tamura
    Nobumichi Tamura
    Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  • Martin Kunz
    Martin Kunz
    Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
    More by Martin Kunz
  • Matthew A. Marcus
    Matthew A. Marcus
    Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  • Yi-Lin Huang
    Yi-Lin Huang
    Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States
    More by Yi-Lin Huang
  • Chunjuan Zhang
    Chunjuan Zhang
    Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States
  • Bryan W. Eichhorn*
    Bryan W. Eichhorn
    Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States
    *Email: [email protected]
  • , and 
  • Zhi Liu*
    Zhi Liu
    School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
    Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
    State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China
    *Email: [email protected]
    More by Zhi Liu
Cite this: ACS Appl. Mater. Interfaces 2020, 12, 28, 31514–31521
Publication Date (Web):June 19, 2020
https://doi.org/10.1021/acsami.0c08284
Copyright © 2020 American Chemical Society
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Abstract

Cerium oxide (ceria, CeO2) is a technologically important material for energy conversion applications. Its activities strongly depend on redox states and oxygen vacancy concentration. Understanding the functionality of chemical active species and behavior of oxygen vacancy during operation, especially in high-temperature solid-state electrochemical cells, is the key to advance future material design. Herein, the structure evolution of ceria is spatially resolved using bulk-sensitive operando X-ray diffraction and spectroscopy techniques. During water electrolysis, ceria undergoes reduction, and its oxygen non-stoichiometry shows a dependence on the electrochemical current. Cerium local bonding environments vary concurrently to accommodate oxygen vacancy formation, resulting in changes in Ce–O coordination number and Ce3+/Ce4+ redox couple. When reduced enough, a crystallographic phase transition occurs from α to an α′ phase with more oxygen vacancies. Nevertheless, the transition behavior is intriguingly different from the one predicted in the standard phase diagram of ceria. This paper demonstrates a feasible means to control oxygen non-stoichiometry in ceria via electrochemical potential. It also sheds light on the mechanism of phase transitions induced by electrochemical potential. For electrochemical systems, effects from a large-scale electrical environment should be taken into consideration, besides effective oxygen partial pressure and temperature.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c08284.

  • Anton-Paar DHS heater during operando measurement, current–voltage profile, simulation of powder diffraction patterns at 611 °C, relative intensity of α and α′ phases as a function of 2 – x, coherent domain size of the two phases as a function of respective intensity, evolution of relative intensity and 2 – x value of α′ as a function of WT, position limits of α′ phase, powder diffraction patterns, calibration of WT, oxygen non-stoichiometry calculation, refinement results for 611 °C at OCV, applied potentials of +0.3, +0.6, +0.9, and +1.2 V, refinement results for an applied potential of +1.2 V at 511–661 °C, data processing from XAS measurements, k2-weighted Ce L3 EXAFS spectra, and corresponding Fourier transform results (PDF)

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Cited By


This article is cited by 3 publications.

  1. Rishi G. Agarwal, Hyun-Jo Kim, James M. Mayer. Nanoparticle O–H Bond Dissociation Free Energies from Equilibrium Measurements of Cerium Oxide Colloids. Journal of the American Chemical Society 2021, 143 (7) , 2896-2907. https://doi.org/10.1021/jacs.0c12799
  2. S. Patnaik, D.A. Lopes, B.W. Spencer, T.M. Besmann, E. Roberts, T.W. Knight. Evaluation of ceria as a surrogate material for UO2 in experiments on fuel cracking driven by resistive heating. Nuclear Engineering and Design 2021, 384 , 111482. https://doi.org/10.1016/j.nucengdes.2021.111482
  3. Claire Chunjuan Zhang, Shiang Sung, Sage Hartlaub, Ivan Petrovic, Bilge Yilmaz. Example on the Use of Operando Spectroscopy for Developing Mechanistic Insights into Industrial Catalysts and Catalytic Processes. Catalysts 2021, 11 (2) , 200. https://doi.org/10.3390/catal11020200