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 ($$\textit{c}$$ = 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.
- Authors:
-
[2];
[2];
[2];
[2];
[2];
[1]
- 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)
- 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., Spano, Tyler L., Ambrogio, Michael W., Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., and Anderson, Brian B. Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O. United States: N. p., 2019.
Web. doi:10.1039/C9DT02835H.
Kirkegaard, Marie C., Spano, Tyler L., Ambrogio, Michael W., Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., & Anderson, Brian B. Formation of a uranyl hydroxide hydrate via hydration of [(UO2F22O)]7·4H2O. United States. https://doi.org/10.1039/C9DT02835H
Kirkegaard, Marie C., Spano, Tyler L., Ambrogio, Michael W., Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., and Anderson, Brian B. 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 Spano, Tyler L. and Ambrogio, Michael W. and Niedziela, Jennifer L. and Miskowiec, Andrew J. and Shields, Ashley E. and Anderson, Brian B.},
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 ($\textit{c}$ = 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.},
doi = {10.1039/C9DT02835H},
journal = {Dalton Transactions},
number = 36,
volume = 48,
place = {United States},
year = {2019},
month = {8}
}
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy
journal, November 2018
- Lu, Grace; Haes, Amanda J.; Forbes, Tori Z.
- Coordination Chemistry Reviews, Vol. 374
Raman microspectrometric identification of corrosion products formed on UO2 nuclear fuel during leaching experiments
journal, December 2002
- Amme, M.; Renker, B.; Schmid, B.
- Journal of Nuclear Materials, Vol. 306, Issue 2-3
A Raman spectroscopic study of the uranyl carbonate rutherfordine
journal, January 2007
- Frost, Ray L.; Čejka, Jiří
- Journal of Raman Spectroscopy, Vol. 38, Issue 11
Neptunium incorporation in sodium-substituted metaschoepite
journal, April 2007
- Klingensmith, A. L.; Deely, K. M.; Kinman, W. S.
- American Mineralogist, Vol. 92, Issue 4
The crystal structure of uranyl-oxide mineral schoepite, [(UO2)4O (OH)6]( H2O)6, revisited
journal, May 2018
- Plášil, J.
- Journal of Geosciences
Structure of uranium(VI) oxide dihydrate, UO 3 ·2H 2 O; synthetic meta -schoepite (UO 2 ) 4 O(OH) 6 ·5H 2 O
journal, August 2000
- Weller, Mark. T.; Light, Mark E.; Gelbrich, Thomas
- Acta Crystallographica Section B Structural Science, Vol. 56, Issue 4
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Interaction of water with a metal surface: Importance of van der Waals forces
journal, March 2010
- Hamada, Ikutaro; Lee, Kyuho; Morikawa, Yoshitada
- Physical Review B, Vol. 81, Issue 11
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
Infrared spectra of some uranyl nitrate complexes
journal, September 1967
- Bullock, J. I.
- Journal of Inorganic and Nuclear Chemistry, Vol. 29, Issue 9
The structure of the α form of uranyl hydroxide
journal, June 1971
- Taylor, J. C.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 6
Elucidation of the Structure and Vibrational Spectroscopy of Synthetic Metaschoepite and Its Dehydration Product
journal, May 2019
- Kirkegaard, Marie C.; Niedziela, J. L.; Miskowiec, Andrew
- Inorganic Chemistry, Vol. 58, Issue 11
Parametric Time Warping
journal, January 2004
- Eilers, Paul H. C.
- Analytical Chemistry, Vol. 76, Issue 2
Paulscherrerite from the Number 2 Workings, Mount Painter Inlier, Northern Flinders Ranges, South Australia: "Dehydrated schoepite" is a mineral after all
journal, February 2011
- Brugger, J.; Meisser, N.; Etschmann, B.
- American Mineralogist, Vol. 96, Issue 2-3
Water wetting on representative metal surfaces: Improved description from van der Waals density functionals
journal, January 2012
- Hamada, Ikutaro; Meng, Sheng
- Chemical Physics Letters, Vol. 521
Infrared spectra of rutherfordine and sharpite
journal, January 1979
- Urbanec, Zdeněk; Čejka, Jiří
- Collection of Czechoslovak Chemical Communications, Vol. 44, Issue 1
Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide
journal, May 2018
- Kirkegaard, Marie C.; Miskowiec, Andrew; Ambrogio, Michael W.
- Inorganic Chemistry, Vol. 57, Issue 10
The crystal structure of ianthinite, [U24+(UO2)4O6(OH)4(H2O)4](H2O)5: a possible phase for Pu4+ incorporation during the oxidation of spent nuclear fuel
journal, October 1997
- Burns, Peter C.; Finch, Robert J.; Hawthorne, Frank C.
- Journal of Nuclear Materials, Vol. 249, Issue 2-3
Study of the thermal stability of studtite by in situ Raman spectroscopy and DFT calculations
journal, March 2017
- Colmenero, Francisco; Bonales, Laura J.; Cobos, Joaquín
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 174
Insight into Hydrogen Bonding of Uranyl Hydroxide Layers and Capsules by Use of 1 H Magic-Angle Spinning NMR Spectroscopy
journal, May 2016
- Alam, Todd M.; Liao, Zuolei; Nyman, May
- The Journal of Physical Chemistry C, Vol. 120, Issue 19
The Transformation of Uranyl Oxide Hydrates: The Effect of Dehydration on Synthetic Metaschoepite and Its Alteration to Becquerelite
journal, October 1999
- Sowder, A. G.; Clark, S. B.; Fjeld, R. A.
- Environmental Science & Technology, Vol. 33, Issue 20
Investigation of the polymorphs and hydrolysis of uranium trioxide
journal, August 2012
- Sweet, Lucas E.; Blake, Thomas A.; Henager, Charles H.
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 296, Issue 1
Correlation of O-H stretching frequencies and O-H…O hydrogen bond lengths in minerals
journal, August 1999
- Libowitzky, Engen
- Monatshefte für Chemie / Chemical Monthly, Vol. 130, Issue 8