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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

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 UO 2 2 + 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. doi: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. doi: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}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.3389/fchem.2019.00583

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Cited by: 4 works
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    Works referencing / citing this record:

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