Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

We have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorin...

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Bibliographic Details
Published in:Inorganic chemistry 2018-05, Vol.57 (10), p.5711-5715
Main Authors: Kirkegaard, Marie C, Miskowiec, Andrew, Ambrogio, Michael W, Anderson, Brian B
Format: Article
Language:English
Subjects:
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary:We have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.8b00512