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

doi:10.1021/acs.inorgchem.8b00434

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: 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.

Authors:

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

Publication Date:: 2018-04-02

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.  doi: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.  doi: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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DOI: 10.1021/acs.inorgchem.8b00434

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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
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Understanding the Stability of Salt-Inclusion Phases for Nuclear Waste-forms through Volume-based Thermodynamics
journal, October 2018

Moore, Emily E.; Kocevski, Vancho; Juillerat, Christian A.
Scientific Reports, Vol. 8, Issue 1
DOI: 10.1038/s41598-018-32903-3

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
DOI: 10.1039/c8dt04675a

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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

Citation Formats

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

Understanding the Stability of Salt-Inclusion Phases for Nuclear Waste-forms through Volume-based Thermodynamics journal, October 2018

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

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

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

Understanding the Stability of Salt-Inclusion Phases for Nuclear Waste-forms through Volume-based Thermodynamics
journal, October 2018

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