Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O

Kirkegaard, Marie C.; Spano, Tyler L.; Ambrogio, Michael W.; Niedziela, Jennifer L.; Miskowiec, Andrew J.; Shields, Ashley E.; Anderson, Brian B.

doi:10.1039/C9DT02835H

Title: Formation of a uranyl hydroxide hydrate via hydration of [(UO₂F_{2₂O)]₇·4H₂O}

Journal Article · Fri Aug 30 00:00:00 EDT 2019 · Dalton Transactions

DOI:https://doi.org/10.1039/C9DT02835H· OSTI ID:1607115

Kirkegaard, Marie C. ^[1];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Hydrated uranyl fluoride, [(UO₂F₂)(H₂O)]₇·4H₂O, is not stable at elevated water vapor pressure, undergoing a complete loss of fluorine to form a uranyl hydroxide hydrate. Powder X-ray diffraction data of the resultant uranyl hydroxide species is presented for the first time, along with Raman and infrared (IR) spectra. The new uranyl hydroxide species is structurally similar to the layered uranyl hydroxide hydrate minerals schoepite and metaschoepite, but has a significantly expanded interlayer spacing ($$\textit{c}$$ = 15.12 vs. 14.73 Å), suggesting that additional H₂O molecules may be present between the uranyl layers. Comparison of the Raman and IR spectra of this new uranyl hydroxide hydrate and synthetic metaschoepite ([(UO₂)₄O(OH)₆]·5H₂O) suggests that the equatorial environment of the uranyl ion may differ and that H₂O molecules in the new species participate in stronger hydrogen bonds. In addition, the interlayer spacing of both this new uranyl hydroxide species and synthetic metaschoepite is shown to be sensitive to the environmental humidity, contracting and re-expanding with desiccation and rehydration. Here, structural distinction between the new uranyl hydroxide species and synthetic metaschoepite is confirmed by a comparison of the thermal behavior; unlike metaschoepite, the new hydrate does not form α-UO₂(OH)₂ upon dehydration.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC05-00OR22725; 2012-DN-130-NF0001

OSTI ID:: 1607115

Alternate ID(s):: OSTI ID: 1562317

Journal Information:: Dalton Transactions, Vol. 48, Issue 36; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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