Structural Changes in Ce0.5Zr0.5O2−δ under Temperature-Swing and Isothermal Solar Thermochemical Looping Conditions Determined by in Situ Ce K and Zr K Edge X-ray Absorption Spectroscopy

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• 作者：Matthäus Rothensteiner ; Alexander Bonk ; Ulrich F. Vogt ; Hermann Emerich ; Jeroen A. van Bokhoven
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：July 7, 2016
• 年：2016
• 卷：120
• 期：26
• 页码：13931-13941
• 全文大小：623K
• 年卷期：0
• ISSN：1932-7455

文摘

Structural changes in an equimolar ceria–zirconia solid solution were determined from room temperature to 1773 K under typical reducing and oxidizing conditions in a reactor for the solar thermochemical dissociation of water or carbon dioxide in a two-step redox cycle. We report the first in situ X-ray absorption spectroscopy (XAS) measurements at both the Ce K and Zr K edges under the conditions of thermochemical carbon dioxide splitting and a temperature swing of 1773 to 1073 K and isothermal conditions at 1773 K. The shift in the Ce K absorption edge reveals quantitative information about changes in the electronic structure of cerium. The maximum extent of reduction at 1773 K was 53% ± 5%; about 9% ± 5% of the cerium atoms changed valence from 4+ to 3+ and vice versa during isothermal looping in a flow of argon and carbon dioxide, respectively. Zr K edge XANES indicated a transformation of the oxygen coordination of zirconia to a more centrosymmetric cubic geometry upon reduction. During isothermal cycling at 1773 K, there were no visible changes in the zirconium–oxygen coordination geometry.