Journal article
A review of defect structure and chemistry in ceria and its solid solutions.
- Schmitt R Electrochemical Materials, Department of Materials, ETH Zurich, Switzerland.
- Nenning A Electrochemical Materials, Department of Materials, ETH Zurich, Switzerland and Electrochemical Materials, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. jrupp@mit.edu and TU Wien, Institute of Chemical Technologies and Analytics, Vienna, 1060, Austria.
- Kraynis O Department Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel.
- Korobko R Electrochemical Materials, Department of Materials, ETH Zurich, Switzerland and Department Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel.
- Frenkel AI Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY 11794, USA.
- Lubomirsky I Department Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel.
- Haile SM Materials Science and Engineering, Northwestern University, Evanston, IL, USA.
- Rupp JLM Electrochemical Materials, Department of Materials, ETH Zurich, Switzerland and Electrochemical Materials, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. jrupp@mit.edu and Electrochemical Materials, Department of Electrical Engineering & Computer Science, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
- 2019-12-25
Published in:
- Chemical Society reviews. - 2020
English
Ceria and its solid solutions play a vital role in several industrial processes and devices. These include solar energy-to-fuel conversion, solid oxide fuel and electrolyzer cells, memristors, chemical looping combustion, automotive 3-way catalysts, catalytic surface coatings, supercapacitors and recently, electrostrictive devices. An attractive feature of ceria is the possibility of tuning defect-chemistry to increase the effectiveness of the materials in application areas. Years of study have revealed many features of the long-range, macroscopic characteristics of ceria and its derivatives. In this review we focus on an area of ceria defect chemistry which has received comparatively little attention - defect-induced local distortions and short-range associates. These features are non-periodic in nature and hence not readily detected by conventional X-ray powder diffraction. We compile the relevant literature data obtained by thermodynamic analysis, Raman spectroscopy, and X-ray absorption fine structure (XAFS) spectroscopy. Each of these techniques provides insight into material behavior without reliance on long-range periodic symmetry. From thermodynamic analyses, association of defects is inferred. From XAFS, an element-specific probe, local structure around selected atomic species is obtained, whereas from Raman spectroscopy, local symmetry breaking and vibrational changes in bonding patterns is detected. We note that, for undoped ceria and its solid solutions, the relationship between short range order and cation-oxygen-vacancy coordination remains a subject of active debate. Beyond collating the sometimes contradictory data in the literature, we strengthen this review by reporting new spectroscopy results and analysis. We contribute to this debate by introducing additional data and analysis, with the expectation that increasing our fundamental understanding of this relationship will lead to an ability to predict and tailor the defect-chemistry of ceria-based materials for practical applications.
- Language
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- English
- Open access status
- hybrid
- Identifiers
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- DOI 10.1039/c9cs00588a
- PMID 31872840
- Persistent URL
- https://folia.unifr.ch/global/documents/175234
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