Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth
Abstract
We report single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs11[(UO2)12(PO4)3O13] (1) and Rb11[UO2)12(PO4)3O12F2] (2) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U3O8, while Cs4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (3) and Rb4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (4) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2-4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase (1) and in contrast an oxyfluoride phase for the Rb containing phase (2). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the uranyl group.
- Authors:
- Publication Date:
- Research Org.:
- Univ. of South Carolina, Columbia, SC (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Hierarchical Waste Form Materials (CHWM)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1564451
- Alternate Identifier(s):
- OSTI ID: 1612658
- Grant/Contract Number:
- SC0016574; 1250052
- Resource Type:
- Published Article
- Journal Name:
- Frontiers in Chemistry
- Additional Journal Information:
- Journal Name: Frontiers in Chemistry Journal Volume: 7; Journal ID: ISSN 2296-2646
- Publisher:
- Frontiers Research Foundation
- Country of Publication:
- Switzerland
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; flux crystal growth; uranyl; phosphuranylite; single crystal; DFT
Citation Formats
Juillerat, Christian A., Kocevski, Vancho, Besmann, Theodore M., and zur Loye, Hans-Conrad. Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth. Switzerland: N. p., 2019.
Web. doi:10.3389/fchem.2019.00583.
Juillerat, Christian A., Kocevski, Vancho, Besmann, Theodore M., & zur Loye, Hans-Conrad. Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth. Switzerland. https://doi.org/10.3389/fchem.2019.00583
Juillerat, Christian A., Kocevski, Vancho, Besmann, Theodore M., and zur Loye, Hans-Conrad. Wed .
"Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth". Switzerland. https://doi.org/10.3389/fchem.2019.00583.
@article{osti_1564451,
title = {Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth},
author = {Juillerat, Christian A. and Kocevski, Vancho and Besmann, Theodore M. and zur Loye, Hans-Conrad},
abstractNote = {We report single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs11[(UO2)12(PO4)3O13] (1) and Rb11[UO2)12(PO4)3O12F2] (2) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U3O8, while Cs4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (3) and Rb4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (4) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2-4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase (1) and in contrast an oxyfluoride phase for the Rb containing phase (2). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the UO22+ uranyl group.},
doi = {10.3389/fchem.2019.00583},
journal = {Frontiers in Chemistry},
number = ,
volume = 7,
place = {Switzerland},
year = {2019},
month = {8}
}
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https://doi.org/10.3389/fchem.2019.00583
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