A Family of Layered Phosphates Crystallizing in a Rare Geometrical Isomer of the Phosphuranylite Topology: Synthesis, Characterization, and Computational Modeling of A4[(UO2)3O2(PO4)2] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange

Juillerat, Christian A.; Moore, Emily E.; Kocevski, Vancho; Besmann, Theodore; zur Loye, Hans-Conrad

doi:10.1021/acs.inorgchem.8b00434

A Family of Layered Phosphates Crystallizing in a Rare Geometrical Isomer of the Phosphuranylite Topology: Synthesis, Characterization, and Computational Modeling of A₄[(UO₂)₃O₂(PO₄)₂] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange

Journal Article · Mon Apr 02 00:00:00 EDT 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b00434· OSTI ID:1470523

Juillerat, Christian A. ^[1]; Moore, Emily E. ^[1]; ^[1]; Besmann, Theodore ^[1]; ^[1]

Univ. of South Carolina, Columbia, SC (United States). The Center for Hierarchical Wasteform Materials

Single crystals of eight new layered uranyl phosphates were grown from alkali chloride fluxes: Cs_1.4K_2.6[(UO₂)₃O₂(PO₄)₂], Cs_0.7K_3.3[(UO₂)₃O₂(PO₄)₂], Rb_1.4K_2.6[(UO₂)₃O₂(PO₄)₂], K₄[(UO₂)₃O₂(PO₄)₂], K_2.9Na_0.9Rb_0.2[(UO₂)₃O₂(PO₄)₂], K_2.1Na_0.7Rb_1.2[(UO₂)₃O₂(PO₄)₂], Cs_1.7K_4.3[(UO₂)₅O₅(PO₄)₂], and Rb_1.6K_4.4[(UO₂)₅O₅(PO₄)₂]. All structures crystallize in the monoclinic space group, P2₁/c and contain uranyl phosphate layers with alkali metals located between the layers for charge balance. Ion exchange experiments on Cs_0.7K_3.3[(UO₂)₃O₂(PO₄)₂], Rb_1.4K_2.6[(UO₂)₃O₂(PO₄)₂], and K₄[(UO₂)₃O₂(PO₄)₂] demonstrated that Cs and Rb cations cannot be exchanged for K cations; however, K cations can be readily exchanged for Na, Rb, and Cs. Enthalpies of formation were calculated from density functional theory (DFT) and volume-based thermodynamics (VBT) for all six structures. A value for the enthalpy of formation of the phosphuranylite sheet, [(UO₂)₃O₂(PO₄)₂]^4–, was derived using single-ion additive methods coupled with VBT. Finally, DFT and VBT calculations were used to justify results of the ion exchange experiments. Cs_0.7K_3.3[(UO₂)₃O₂(PO₄)₂], Rb_1.4K_2.6[(UO₂)₃O₂(PO₄)₂], and K₄[(UO₂)₃O₂(PO₄)₂] exhibit typical luminescence of the uranyl group.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC), Washington D.C. (United States). Center for Hierarchical Waste Form Materials (CHWM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0016574

OSTI ID:: 1470523

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 8 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Flux crystal growth: a versatile technique to reveal the crystal chemistry of complex uranium oxides Juillerat, Christian A.; Klepov, Vladislav V.; Morrison, Gregory Dalton Transactions, Vol. 48, Issue 10 https://doi.org/10.1039/c8dt04675a	journal	January 2019
Targeted crystal growth of uranium gallophosphates via the systematic exploration of the UF ₄ –GaPO ₄ –ACl (A = Cs, Rb) phase space Juillerat, Christian A.; Klepov, Vladislav V.; Smith, Mark D. CrystEngComm, Vol. 22, Issue 17 https://doi.org/10.1039/d0ce00343c	journal	January 2020

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CSD 1823655: Experimental Crystal Structure Determination Juillerat, C. A.; Moore, E. E.; Kocevski, V. https://doi.org/10.25505/fiz.icsd.cc1z6nlf The current record is supplemented by this dataset	dataset	January 2018
CSD 1823656: Experimental Crystal Structure Determination Juillerat, C. A.; Moore, E. E.; Kocevski, V. https://doi.org/10.25505/fiz.icsd.cc1z6nmg The current record is supplemented by this dataset	dataset	January 2018
CSD 1588580: Experimental Crystal Structure Determination A., Juillerat, C.; E., Moore, E.; V., Kocevski, https://doi.org/10.5517/ccdc.csd.cc1qb1jm The current record is supplemented by this dataset	dataset	January 2018
CSD 1588581: Experimental Crystal Structure Determination A., Juillerat, C.; E., Moore, E.; V., Kocevski, https://doi.org/10.5517/ccdc.csd.cc1qb1kn The current record is supplemented by this dataset	dataset	January 2018
CSD 1588582: Experimental Crystal Structure Determination A., Juillerat, C.; E., Moore, E.; V., Kocevski, https://doi.org/10.5517/ccdc.csd.cc1qb1lp The current record is supplemented by this dataset	dataset	January 2018
CSD 1588583: Experimental Crystal Structure Determination A., Juillerat, C.; E., Moore, E.; V., Kocevski, https://doi.org/10.5517/ccdc.csd.cc1qb1mq The current record is supplemented by this dataset	dataset	January 2018
CSD 1588584: Experimental Crystal Structure Determination A., Juillerat, C.; E., Moore, E.; V., Kocevski, https://doi.org/10.5517/ccdc.csd.cc1qb1nr The current record is supplemented by this dataset	dataset	January 2018
CSD 1588585: Experimental Crystal Structure Determination A., Juillerat, C.; E., Moore, E.; V., Kocevski, https://doi.org/10.5517/ccdc.csd.cc1qb1ps The current record is supplemented by this dataset	dataset	January 2018