A review of defect structure and chemistry in ceria and its solid solutions
Name
c9cs00588a.pdf
Description
Published version
Size
9.17 MB
Format
Adobe PDF
Checksum (MD5)
ddb49794deed9aee67025780deb7ec03
Author(s)
Schmitt, Rafael
Nenning, Andreas
Kraynis, Olga
Korobko, Roman
Frenkel, Anatoly I.
Lubomirsky, Igor
Haile, Sossina M.
Rupp, Jennifer Lilia Marguerite
Date Issued
December 2019
Journal
Chemical Society Reviews
Publisher
Royal Society of Chemistry (RSC)
Citation
Schmitt, Rafael et al. "A review of defect structure and chemistry in ceria and its solid solutions." Chemical Society Reviews 49, 2 (January 2020): 554-592 © 2020 Royal Society of Chemistry
Version
Final published version
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Terms of Use
Creative Commons Attribution Noncommercial 3.0 unported license
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1039/c9cs00588a
