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Front. Chem. | doi: 10.3389/fchem.2019.00583

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

 Christian A. Juillerat1,  Hans-Conrad zur Loye1*, Theodore M. Besmann1 and Vancho Kocevski1
  • 1University of South Carolina, United States

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.

Keywords: Flux crystal growth, Uranyl, Phosphuranylite, single crystal, DFT

Received: 26 Jun 2019; Accepted: 02 Aug 2019.

Edited by:

Federico Cesano, University of Turin, Italy

Reviewed by:

Francis ABRAHAM, Université de Lille, France
Shuao Wang, Soochow University, China  

Copyright: © 2019 Juillerat, zur Loye, Besmann and Kocevski. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

* Correspondence: Mx. Hans-Conrad zur Loye, University of South Carolina, Columbia, United States, zurloye@mailbox.sc.edu