Gamma-Ray-Induced Formation of Uranyl Peroxide Cage Clusters

Daniel E. Felton, Melissa Fairley, Ana Arteaga, May Nyman, Jay A. Laverne, Peter C. Burns

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Aqueous solutions of lithium uranyl triperoxide, Li4[UO2(O2)3] (LiUT), were irradiated with gamma rays at room temperature and found to form the uranyl peroxide cage cluster, Li24[(UO2)(O2)(OH)]24 (Li-U24). Raman spectroscopy and 18O labeling were used to identify the Raman-active vibrations of LiUT. With these assignments, the concentration of LiUT was tracked as a function of radiation dose. A discrepancy between monomer removal and cluster formation suggests that the reaction proceeds by the assembly of an intermediate. Non-negative matrix factorization was used to separate Raman spectra into components and resulted in the identification of a unique intermediate species. Much of the conversion appears to be driven by water radiolysis products, particularly the hydroxyl radical. This differs from the 18O-labeled copper-catalyzed formation of U24, which progresses at a steady rate with no observation of intermediates. Li-U24 in solution decomposes at high radiation doses resulting in a solid insoluble product similar to Na-compreignacite, Na2(UO2)6O4(OH)6·7H2O, which contains uranyl oxyhydroxy sheets.

Original languageEnglish
Pages (from-to)11916-11922
Number of pages7
JournalInorganic Chemistry
Volume61
Issue number30
DOIs
StatePublished - Aug 1 2022
Externally publishedYes

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