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Isotopic Oxygen Exchange between CeO 2 and O 2 : A Heteroexchange Mechanism
Author(s) -
Han Jun,
Chen Dandan,
Zhu Jun
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201903770
Subject(s) - density functional theory , reaction mechanism , oxygen , materials science , mechanism (biology) , chemistry , computational chemistry , catalysis , physics , biochemistry , organic chemistry , quantum mechanics
Isotopic oxygen exchange (IOE) is a crucial reaction required in the purification of 238 PuO 2 which has been used as an important fuel in space exploration. Experimental studies on the IOE between 238 PuO 2 and O 2 are costly and hazardous due to the radioactivity. With extremely similar crystal structures, CeO 2 could be a fair surrogate for 238 PuO 2 in the investigation of physicochemical properties. Here, we perform density functional theory calculations to simulate the IOE between CeO 2 and O 2 , wherein a heteroexchange mechanism is proposed. Estimated reaction barriers for CeO 2 /O 2 and 238 PuO 2 /O 2 systems are comparable (25.8 and 29.3 kcal mol −1 respectively), indicating CeO 2 is a potential substitute for 238 PuO 2 in an IOE reaction. Our study could be useful for experimental chemists to probe more complicated IOE mechanisms for both CeO 2 /O 2 and PuO 2 /O 2 .