Radiation-Induced Solid-State Transformations of Uranyl Peroxides

Fairley, Melissa; Felton, Daniel E.; Sigmon, Ginger E.; Szymanowski, Jennifer E. S.; Poole, Nicholas A.; Nyman, May; Burns, Peter C.; LaVerne, Jay A.

doi:10.1021/acs.inorgchem.1c02603

Radiation-Induced Solid-State Transformations of Uranyl Peroxides

Journal Article · Wed Dec 29 00:00:00 EST 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c02603· OSTI ID:1838189

^[1]; Felton, Daniel E. ^[2]; Sigmon, Ginger E. ^[2]; Szymanowski, Jennifer E. S. ^[2]; Poole, Nicholas A. ^[2]; ^[3]; ^[2]; ^[2]

Univ. of Notre Dame, IN (United States); University of Notre Dame
Univ. of Notre Dame, IN (United States)
Oregon State Univ., Corvallis, OR (United States)

Single-crystal X-ray diffraction studies of pristine and γ-irradiated Ca₂[UO₂(O₂)₃]·9H₂O reveal site-specific atomic-scale changes during the solid-state progression from a crystalline to X-ray amorphous state with increasing dose. Following γ-irradiation to 1, 1.5, and 2 MGy, the peroxide group not bonded to Ca²⁺ is progressively replaced by two hydroxyl groups separated by 2.7 Å (with minor changes in the unit cell), whereas the peroxide groups bonded to Ca²⁺ cations are largely unaffected by irradiation prior to amorphization, which occurs by a dose of 3 MGy. The conversion of peroxide to hydroxyl occurs through interaction of neighboring lattice H₂O molecules and ionization of the peroxide O–O bond, which produces two hydroxyls, and allows isolation of the important monomer building block, UO₂(O₂)₂(OH)₂^4–, that is ubiquitous in uranyl capsule polyoxometalates. Steric crowding in the equatorial plane of the uranyl ion develops and promotes transformation to an amorphous phase. In contrast, γ-irradiation of solid Li₄[(UO₂)(O₂)₃]·10H₂O results in a solid-state transformation to a well-crystallized peroxide-free uranyl oxyhydrate containing sheets of equatorial edge and vertex-sharing uranyl pentagonal bipyramids with likely Li and H₂O in interlayer positions. The irradiation products of these two uranyl triperoxide monomers are compared via X-ray diffraction (single-crystal and powder) and Raman spectroscopy, with a focus on the influence of the Li⁺ and Ca²⁺ countercations. Highly hydratable and mobile Li+ yields to uranyl hydrolysis reactions, while Ca²⁺ provides lattice rigidity, allowing observation of the first steps of radiation-promoted transformation of uranyl triperoxide.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FC02-04ER15533; NA0003763

OSTI ID:: 1838189

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 2 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Radiation-Induced Solid-State Transformations of Uranyl Peroxides

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