November 2023

Journal

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

By:
Kirkegaard, Marie C; Miskowiec, Andrew J; Ambrogio, Michael W; Anderson, Brian B
Journal Name:
Inorganic Chemistry
Page Number:
5711-5715
Volume:
57
Issue Number:
10
Publication Date:
November 9, 2023
View DOI Listing:
https://doi.org/10.1021/acs.inorgchem.8b00512

Abstract

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.