A review of defect structure and chemistry in ceria and its solid solutions
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 re...
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| Published in | Chemical Society reviews Vol. 49; no. 2; pp. 554 - 592 |
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| Main Authors | , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
21.01.2020
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| Subjects | |
| Online Access | Get full text |
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| Summary: | 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.
Doped and oxygen deficient ceria exhibits local bonding patterns that deviate from the average fluorite symmetry found in XRD. |
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| Bibliography: | Anatoly Frenkel is a Professor in the Department of Materials Science and Chemical Engineering at Stony Brook University and a Senior Chemist at the Division of Chemistry, Brookhaven National Laboratory. He was a Professor and Chair, Physics Department at Yeshiva University, and a Research Scientist at the University of Illinois at Urbana-Champaign. He received MSc degree from St. Petersburg University and PhD degree from Tel Aviv University, all in Physics. His research interests focus on development and application of synchrotron methods for structural analysis and design of nanomaterials. He is a Fellow of the American Physical Society. Rafael Schmitt is currently working on the industrialization of additive manufacturing with a focus on ceramic and metallic materials at Exentis Group AG in Stetten, Switzerland. He earned his PhD degree at ETH Zurich in 2017 in the group of electrochemical materials of Prof. Jennifer L. M. Rupp. He worked on understanding the mass and charge transport in oxide-based resistive switching materials under high electric fields in view of providing design guidelines for memristive devices. Awards include the Excellence Scholarship & Opportunity Programme for the Master's degree at ETH Zurich and the E-MRS Young Scientist Award at the E-MRS Spring Meeting in Lille, France, 2016. Olga Kraynis is currently a postdoctoral researcher at the Department of Materials and Interfaces at the Weizmann Institute of Science (WIS) Israel, in the group of Prof. Igor Lubomirsky. She received a BSc in chemistry from Tel Aviv University (Israel) in 2012. She then completed her PhD in the group of Prof. Igor Lubomirsky at the WIS in 2019. The topic of her doctoral thesis was structural characterization of point defects, and their effect on mechanic and electro-mechanic properties of ceria thin film materials. Olga Kraynis is the recipient of the 2019 Professor Israel Dostrovsky Memorial Prize of Excellence. Sossina Haile is the Walter P. Murphy Professor of Materials Science and Engineering at Northwestern University. She earned her PhD in Materials Science and Engineering from the Massachusetts Institute of Technology in 1992. Haile's research broadly encompasses materials for sustainable electrochemical energy technologies. Amongst her many awards, in 2008 Haile received an American Competitiveness and Innovation Fellowship from the U.S. National Science Foundation. She is a fellow of the Materials Research Society, the American Ceramics Society, the African Academy of Sciences, and the Ethiopian Academy of Sciences, and serves on the editorial boards of Materials Horizons and Annual Review of Materials Research. Andreas Nenning is currently a postdoctoral researcher at TU Wien, investigating the electrochemical properties and redox kinetics of acceptor doped ceria for use in solid oxide fuel cells. In 2016 and 2017, he worked in the electrochemical materials group of Prof. Jennifer Rupp, and later with her at MIT. There his work focused on the observation of ionic and electronic conduction in Gd-doped ceria as a model system for electrochemical valence change resistive memories. Another research topic was optimization of electrochemical carbon dioxide sensors. He received his PhD degree in 2016 at the TU Vienna, working in Prof. Jürgen Fleig's group. Roman Korobko is a staff scientist at the Solid-State Structural Dynamics group in the Weizmann Institute of Science. His research interests include the elastic, electronic and memristive properties of dielectrics. Roman received his BA in Chemistry and BSc in Materials Engineering in Technion in 2003. He continued his studies in the Faculty of Chemistry of the WIS where he earned MSc in 2009 and PhD on controlling the elastic properties of ceramics with an external electric field in 2014. He then carried out postdoctoral research at the Electrochemical Materials group in ETH Zurich in the field of memristive materials during 2014-2017. Igor Lubomirsky is a professor at the Department of Materials and Interfaces at the Weizmann Institute of Science, Israel. He studied chemical engineering in Kharkov (now Ukraine) and then earned his PhD in the WIS. After postdoctoral terms in UCLA and Max Planck Institute for Solid State Research, he rejoined the WIS as a Chemistry faculty member. His studies focus on solids, in which local symmetry reduction strongly affects mechanical, electromechanical and pyroelectric properties. During the last decade, he initiated studies of anelasticity in solids with a high concentration of point defects. These solids withstand unusually large range of deformations, within which they exhibit rubber-like properties. Jennifer Rupp is the Thomas Lord Associate Professor of Electrochemical Materials at the Department of Materials Science and Engineering and in the Department of Electrical Engineering and Computer Science at MIT. Prior she was a non-tenure track assistant professor at ETH. Her research is in designing "ceramic" materials and their properties for device functions in energy and computation. Rupp and team received several honors such as the Displaying Future Award by the company Merck 2018 for a glucose converting fuel cell chip, BASF and Volkswagen Science Award 2017 for battery research, "Top 40 international scientist under the age of 40" by World Economic Forum 2015 and others. Currently, she is associate editor at the Journal of Materials Chemistry A and board member at Advanced Functional Materials and Advanced Interface Materials. 10.1039/c9cs00588a Electronic supplementary information (ESI) available. See DOI ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 |
| ISSN: | 0306-0012 1460-4744 1460-4744 |
| DOI: | 10.1039/c9cs00588a |