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Title: 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

Abstract

Single crystals of eight new layered uranyl phosphates were grown from alkali chloride fluxes: Cs1.4K2.6[(UO2)3O2(PO4)2], Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(UO2)3O2(PO4)2], K4[(UO2)3O2(PO4)2], K2.9Na0.9Rb0.2[(UO2)3O2(PO4)2], K2.1Na0.7Rb1.2[(UO2)3O2(PO4)2], Cs1.7K4.3[(UO2)5O5(PO4)2], and Rb1.6K4.4[(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 Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(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. Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(UO2)3O2(PO4)2], and K4[(UO2)3O2(PO4)2] exhibit typical luminescence of the uranyl group.

Authors:
 [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Univ. of South Carolina, Columbia, SC (United States). The Center for Hierarchical Wasteform Materials
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington D.C. (United States). Center for Hierarchical Waste Form Materials (CHWM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470523
Grant/Contract Number:  
SC0016574
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 8; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Juillerat, Christian A., Moore, Emily E., Kocevski, Vancho, Besmann, Theodore, and zur Loye, Hans-Conrad. 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. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b00434.
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Juillerat, Christian A., Moore, Emily E., Kocevski, Vancho, Besmann, Theodore, & zur Loye, Hans-Conrad. 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. United States. https://doi.org/10.1021/acs.inorgchem.8b00434
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Juillerat, Christian A., Moore, Emily E., Kocevski, Vancho, Besmann, Theodore, and zur Loye, Hans-Conrad. Mon . "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". United States. https://doi.org/10.1021/acs.inorgchem.8b00434. https://www.osti.gov/servlets/purl/1470523.
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@article{osti_1470523,
title = {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},
author = {Juillerat, Christian A. and Moore, Emily E. and Kocevski, Vancho and Besmann, Theodore and zur Loye, Hans-Conrad},
abstractNote = {Single crystals of eight new layered uranyl phosphates were grown from alkali chloride fluxes: Cs1.4K2.6[(UO2)3O2(PO4)2], Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(UO2)3O2(PO4)2], K4[(UO2)3O2(PO4)2], K2.9Na0.9Rb0.2[(UO2)3O2(PO4)2], K2.1Na0.7Rb1.2[(UO2)3O2(PO4)2], Cs1.7K4.3[(UO2)5O5(PO4)2], and Rb1.6K4.4[(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 Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(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. Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(UO2)3O2(PO4)2], and K4[(UO2)3O2(PO4)2] exhibit typical luminescence of the uranyl group.},
doi = {10.1021/acs.inorgchem.8b00434},
journal = {Inorganic Chemistry},
number = 8,
volume = 57,
place = {United States},
year = {2018},
month = {4}
}
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    Works referencing / citing this record:

    Flux crystal growth: a versatile technique to reveal the crystal chemistry of complex uranium oxides
    journal, January 2019

    • Juillerat, Christian A.; Klepov, Vladislav V.; Morrison, Gregory
    • Dalton Transactions, Vol. 48, Issue 10
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    Understanding the Stability of Salt-Inclusion Phases for Nuclear Waste-forms through Volume-based Thermodynamics
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    Targeted crystal growth of uranium gallophosphates via the systematic exploration of the UF 4 –GaPO 4 –ACl (A = Cs, Rb) phase space
    journal, January 2020

    • Juillerat, Christian A.; Klepov, Vladislav V.; Smith, Mark D.
    • CrystEngComm, Vol. 22, Issue 17
    • DOI: 10.1039/d0ce00343c
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