Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions

doi:10.1021/acs.cgd.7b00997

Title: Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions

Abstract

In this study, a series of novel uranyl borates, K₄Sr₄[(UO₂)₁₃(B₂O₅)₂(BO₃)₂O₁₂], A₆[(UO₂)₁₂(BO₃)₈O₃](H₂O)₆ (A = Rb and Cs), and Rb₃[(UO₂)₃(BO₃)₂O(OH)](H₂O), were synthesized using conventional conditions. Among them, K₄Sr₄[(UO₂)₁₃(B₂O₅)₂(BO₃)₂O₁₂] and A₆[(UO₂)₁₂(BO₃)₈O₃](H₂O)₆ were obtained through a high-temperature solid-state reaction method, whereas Rb₃[(UO₂)₃(BO₃)₂O(OH)](H₂O) was synthesized via a hydrothermal reaction. All compounds adopt novel two-dimensional (2D) layered structures in which basic building units (BBUs) consist of corner- or edge-sharing UO_x (x = 6, 7 and 8) polyhedra linked with planar BO₃ triangles or B₂O₅ dimers. K₄Sr₄[(UO₂)₁₃(B₂O₅)₂(BO₃)₂O₁₂] is the first mixed alkali–alkaline earth metal uranyl borate. This compound has the most complex 2D anion topology observed thus far in 2D uranyl borates. The fundamental building block (FBB) in this structure, [(UO₂)₁₃(B₂O₅)₂(BO₃)₂O₁₂]^12–, consists of 3 UO₈ hexagonal bipyramids and 10 UO₇ pentagonal bipyramids connected with 2 BO₃ triangles and 2 B₂O₅ dimers. The FBB of Rb₆[(UO₂)₁₂(BO₃)₈O₃](H₂O)₆ is [(UO₂)₆(BO₃)₄O₃]^6–, comprised of five edge-sharing UO₇ pentagonal bipyramids, one UO₆ tetragonal bipyramid, and four BO₃ triangles. The simplest FBB, [(UO₂)₃(BO₃)₂O₂]^4–, occurs in Rb₃[(UO₂)₃(BO₃)₂O(OH)](H₂O), where three UO₇ pentagonal bipyramids are linked with two BO₃ triangles via edge sharing. The aforementioned FBBs are further polymerized into the corresponding infinite uranyl borates layers. Finally, the synthetic methods, novel topologies, thermal stability, and spectroscopic propertiesmore »« less

Authors:

Hao, Yucheng ^[1]; Kegler, Philip ^[1]; Bosbach, Dirk ^[1];

^[2];

^[3];

^[4]

Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, Jülich (Germany)
Florida State Univ., Tallahassee, FL (United States)
School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Jiangsu (China)
Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, Jülich (Germany); RWTH Aachen Univ. (Germany)

Publication Date:: 2017-10-20

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1470218

Grant/Contract Number:: SC0016568

Resource Type:: Accepted Manuscript

Journal Name:: Crystal Growth and Design

Additional Journal Information:: Journal Volume: 17; Journal Issue: 11; Journal ID: ISSN 1528-7483

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Hao, Yucheng, Kegler, Philip, Bosbach, Dirk, Albrecht-Schmitt, Thomas E., Wang, Shuao, and Alekseev, Evgeny V. Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.cgd.7b00997.

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                    Hao, Yucheng, Kegler, Philip, Bosbach, Dirk, Albrecht-Schmitt, Thomas E., Wang, Shuao, & Alekseev, Evgeny V. Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions.  United States.  doi:10.1021/acs.cgd.7b00997.

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                    Hao, Yucheng, Kegler, Philip, Bosbach, Dirk, Albrecht-Schmitt, Thomas E., Wang, Shuao, and Alekseev, Evgeny V. Fri .  
        "Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions".  United States.  doi:10.1021/acs.cgd.7b00997.  https://www.osti.gov/servlets/purl/1470218.

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@article{osti_1470218,

  title        = {Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions},

  author       = {Hao, Yucheng and Kegler, Philip and Bosbach, Dirk and Albrecht-Schmitt, Thomas E. and Wang, Shuao and Alekseev, Evgeny V.},

  abstractNote = {In this study, a series of novel uranyl borates, K4Sr4[(UO2)13(B2O5)2(BO3)2O12], A6[(UO2)12(BO3)8O3](H2O)6 (A = Rb and Cs), and Rb3[(UO2)3(BO3)2O(OH)](H2O), were synthesized using conventional conditions. Among them, K4Sr4[(UO2)13(B2O5)2(BO3)2O12] and A6[(UO2)12(BO3)8O3](H2O)6 were obtained through a high-temperature solid-state reaction method, whereas Rb3[(UO2)3(BO3)2O(OH)](H2O) was synthesized via a hydrothermal reaction. All compounds adopt novel two-dimensional (2D) layered structures in which basic building units (BBUs) consist of corner- or edge-sharing UOx (x = 6, 7 and 8) polyhedra linked with planar BO3 triangles or B2O5 dimers. K4Sr4[(UO2)13(B2O5)2(BO3)2O12] is the first mixed alkali–alkaline earth metal uranyl borate. This compound has the most complex 2D anion topology observed thus far in 2D uranyl borates. The fundamental building block (FBB) in this structure, [(UO2)13(B2O5)2(BO3)2O12]12–, consists of 3 UO8 hexagonal bipyramids and 10 UO7 pentagonal bipyramids connected with 2 BO3 triangles and 2 B2O5 dimers. The FBB of Rb6[(UO2)12(BO3)8O3](H2O)6 is [(UO2)6(BO3)4O3]6–, comprised of five edge-sharing UO7 pentagonal bipyramids, one UO6 tetragonal bipyramid, and four BO3 triangles. The simplest FBB, [(UO2)3(BO3)2O2]4–, occurs in Rb3[(UO2)3(BO3)2O(OH)](H2O), where three UO7 pentagonal bipyramids are linked with two BO3 triangles via edge sharing. The aforementioned FBBs are further polymerized into the corresponding infinite uranyl borates layers. Finally, the synthetic methods, novel topologies, thermal stability, and spectroscopic properties of these compounds are reported herein.},

  doi          = {10.1021/acs.cgd.7b00997},

  journal      = {Crystal Growth and Design},

  number       = 11,

  volume       = 17,

  place        = {United States},

  year         = {2017},

  month        = {10}

}

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DOI: 10.1021/acs.cgd.7b00997

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Works referencing / citing this record:

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Title: Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions

Abstract

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