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 A ₄[(UO ₂) ₃O ₂(PO ₄) ₂] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange

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Abstract

Single crystals of eight new layered uranyl phosphates were grown from alkali chloride fluxes: Cs _1.4K _2.6[(UO ₂) ₃O ₂(PO ₄) ₂], Cs _0.7K _3.3[(UO ₂) ₃O ₂(PO ₄) ₂], Rb _1.4K _2.6[(UO ₂) ₃O ₂(PO ₄) ₂], K ₄[(UO ₂) ₃O ₂(PO ₄) ₂], K _2.9Na _0.9Rb _0.2[(UO ₂) ₃O ₂(PO ₄) ₂], K _2.1Na _0.7Rb _1.2[(UO ₂) ₃O ₂(PO ₄) ₂], Cs _1.7K _4.3[(UO ₂) ₅O ₅(PO ₄) ₂], and Rb _1.6K _4.4[(UO ₂) ₅O ₅(PO ₄) ₂]. All structures crystallize in the monoclinic space group, P2 ₁/ 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[(UO ₂) ₃O ₂(PO ₄) ₂], Rb _1.4K _2.6[(UO ₂) ₃O ₂(PO ₄) ₂], and K ₄[(UO ₂) ₃O ₂(PO ₄) 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, [(UO ₂) ₃O ₂(PO ₄) ₂] ^4–, was derived using single-ion additive methodsmore »« less

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) (SC-22)

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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Title: A Family of Layered Phosphates Crystallizing in a Rare Geometrical Isomer of the Phosphuranylite Topology: Synthesis, Characterization, and Computational Modeling of A 4[(UO 2) 3O 2(PO 4) 2] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange

Abstract

Citation Formats

Title: A Family of Layered Phosphates Crystallizing in a Rare Geometrical Isomer of the Phosphuranylite Topology: Synthesis, Characterization, and Computational Modeling of A ₄[(UO ₂) ₃O ₂(PO ₄) ₂] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange