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

Abstract

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 (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.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1607115
Alternate Identifier(s):
OSTI ID: 1562317
Grant/Contract Number:  
AC05-00OR22725; 2012-DN-130-NF0001
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 48; Journal Issue: 36; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Kirkegaard, Marie C., Ambrogio, Michael W., Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., Anderson, Brian B., and Spano, Tyler L. Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O. United States: N. p., 2019. Web. https://doi.org/10.1039/C9DT02835H.
Kirkegaard, Marie C., Ambrogio, Michael W., Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., Anderson, Brian B., & Spano, Tyler L. Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O. United States. https://doi.org/10.1039/C9DT02835H
Kirkegaard, Marie C., Ambrogio, Michael W., Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., Anderson, Brian B., and Spano, Tyler L. Fri . "Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O". United States. https://doi.org/10.1039/C9DT02835H. https://www.osti.gov/servlets/purl/1607115.
@article{osti_1607115,
title = {Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O},
author = {Kirkegaard, Marie C. and Ambrogio, Michael W. and Niedziela, Jennifer L. and Miskowiec, Andrew J. and Shields, Ashley E. and Anderson, Brian B. and Spano, Tyler L.},
abstractNote = {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 (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.},
doi = {10.1039/C9DT02835H},
journal = {Dalton Transactions},
number = 36,
volume = 48,
place = {United States},
year = {2019},
month = {8}
}

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