Na2(UO2)(BO3): An All-Uranium(V) Borate Synthesized under Mild Hydrothermal Conditions

Pace, Kristen A.; Kocevski, Vancho; Karakalos, Stavros G.; Morrison, Gregory; Besmann, Theodore; zur Loye, Hans-Conrad

doi:10.1021/acs.inorgchem.8b00487

Title: Na₂(UO₂)(BO₃): An All-Uranium(V) Borate Synthesized under Mild Hydrothermal Conditions

Journal Article · 01 April 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00487 · OSTI ID:1470521

Pace, Kristen A. ^[1];

^[2];

^[3];

^[1]; Besmann, Theodore ^[2];

^[1]

Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry; Univ. of South Carolina, Columbia, SC (United States). Center for Hierarchical Wasteform Materials
Univ. of South Carolina, Columbia, SC (United States). Center for Hierarchical Wasteform Materials; Univ. of South Carolina, Columbia, SC (United States). Dept. of Mechanical Engineering
Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering

The first entirely pentavalent uranium borate, Na₂(UO₂)(BO₃), was synthesized under mild hydrothermal conditions. The single-crystal structure was solved in the orthorhombic space group Cmcm with a = 10.0472(3) Å, b = 6.5942(2) Å, and c = 6.9569(2) Å. Magnetic susceptibility measurements revealed an antiferromagnetic transition at 12 K and an effective magnetic moment of 2.33 μ_B. Finally, density functional theory calculations indicated dynamic stability of the structure above 0 K.

View Accepted Manuscript (DOE)

Cite

Export

Save

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:: 1470521

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

References (39)

A ₃ (U ₂ O ₄ )(Ge ₂ O ₇ ) (A=Rb, Cs): Mixed-Valence Uranium(V,VI) Germanates Lin, Chia-Hui; Lii, Kwang-Hwa Angewandte Chemie International Edition, Vol. 47, Issue 45 https://doi.org/10.1002/anie.200803658	journal	October 2008
Materials Discovery by Flux Crystal Growth: Quaternary and Higher Order Oxides Bugaris, Daniel E.; zur Loye, Hans-Conrad Angewandte Chemie International Edition, Vol. 51, Issue 16 https://doi.org/10.1002/anie.201102676	journal	January 2012
High-Pressure Synthesis and Characterization of New Actinide Borates, An B ₄ O ₈ ( An =Th, U) Hinteregger, Ernst; Hofer, Thomas S.; Heymann, Gunter Chemistry - A European Journal, Vol. 19, Issue 47 https://doi.org/10.1002/chem.201302378	journal	October 2013
Antiferromagnetic Ordering in CoU2O6 and NiU2O6 Hinatsu, Yukio Journal of Solid State Chemistry, Vol. 114, Issue 2 https://doi.org/10.1006/jssc.1995.1091	journal	February 1995
Atomic many-body effects in the 4f XPS of the U5+ and U4+ cations: part II: consequences of orbital relaxation Bagus, Paul S.; Ilton, Eugene S. Theoretical Chemistry Accounts, Vol. 118, Issue 3 https://doi.org/10.1007/s00214-007-0364-9	journal	July 2007
Single Crystal Growth and Structural Characterization of a Novel Mixed-Valent Ternary Uranium Oxide, K8U7O24 Read, Cory M.; Smith, Mark D.; zur Loye, Hans-Conrad Journal of Chemical Crystallography, Vol. 44, Issue 11-12 https://doi.org/10.1007/s10870-014-0555-x	journal	October 2014
Materials Design and Discovery with High-Throughput Density Functional Theory: The Open Quantum Materials Database (OQMD) Saal, James E.; Kirklin, Scott; Aykol, Muratahan JOM, Vol. 65, Issue 11 https://doi.org/10.1007/s11837-013-0755-4	journal	September 2013
Preparation and crystal structure of NaUO3 and Na11U5O16 Bartram, S. F.; Fryxell, R. E. Journal of Inorganic and Nuclear Chemistry, Vol. 32, Issue 11 https://doi.org/10.1016/0022-1902(70)80187-7	journal	November 1970
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Europium valence control in the hydrothermal synthesis of apatites and borosilicates Heyward, Carla C.; Kimani, Martin M.; Moore, Cheryl A. Journal of Alloys and Compounds, Vol. 656 https://doi.org/10.1016/j.jallcom.2015.08.279	journal	January 2016
XPS spectra of the compounds , and Liu, J. -H.; Van den Berghe, S.; Konstantinović, M. J. Journal of Solid State Chemistry, Vol. 182, Issue 5 https://doi.org/10.1016/j.jssc.2009.02.007	journal	May 2009
Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions Hao, Yucheng; Kegler, Philip; Bosbach, Dirk Crystal Growth & Design, Vol. 17, Issue 11 https://doi.org/10.1021/acs.cgd.7b00997	journal	October 2017
Synthesis and Study of the First Zeolitic Uranium Borate Hao, Yucheng; Klepov, Vladislav V.; Kegler, Philip Crystal Growth & Design, Vol. 18, Issue 1 https://doi.org/10.1021/acs.cgd.7b01487	journal	December 2017
Flux versus Hydrothermal Growth: Polymorphism of A ₂ (UO ₂ )Si ₂ O ₆ (A = Rb, Cs) Morrison, Gregory; Smith, Mark D.; zur Loye, Hans-Conrad Inorganic Chemistry, Vol. 56, Issue 3 https://doi.org/10.1021/acs.inorgchem.6b02931	journal	January 2017
Polarity and Chirality in Uranyl Borates: Insights into Understanding the Vitrification of Nuclear Waste and the Development of Nonlinear Optical Materials Wang, Shuao; Alekseev, Evgeny V.; Ling, Jie Chemistry of Materials, Vol. 22, Issue 6 https://doi.org/10.1021/cm9037796	journal	March 2010
Magnetic Susceptibility of Uranium Complexes Kindra, Douglas R.; Evans, William J. Chemical Reviews, Vol. 114, Issue 18 https://doi.org/10.1021/cr500242w	journal	August 2014
Chemistry of uranium (V) Selbin, Joel; Ortego, J. D. Chemical Reviews, Vol. 69, Issue 5 https://doi.org/10.1021/cr60261a004	journal	October 1969
Cs ₃ UGe ₇ O ₁₈ : A Pentavalent Uranium Germanate Containing Four- and Six-Coordinate Germanium Nguyen, Quang Bac; Chen, Chun-Liang; Chiang, Yun-Wei Inorganic Chemistry, Vol. 51, Issue 6 https://doi.org/10.1021/ic3000872	journal	March 2012
High-Temperature, High-Pressure Hydrothermal Synthesis and Characterization of a Salt-Inclusion Mixed-Valence Uranium(V,VI) Silicate: [Na ₉ F ₂ ][(U ^V O ₂ )(U ^VI O ₂ ) ₂ (Si ₂ O ₇ ) ₂ ] Chang, Yu-Chih; Chang, Wen-Jung; Boudin, Sophie Inorganic Chemistry, Vol. 52, Issue 12 https://doi.org/10.1021/ic400854j	journal	May 2013
Further Evidence for the Stabilization of U(V) within a Tetraoxo Core Stritzinger, Jared T.; Alekseev, Evgeny V.; Polinski, Matthew J. Inorganic Chemistry, Vol. 53, Issue 10 https://doi.org/10.1021/ic500523a	journal	May 2014
Mild Hydrothermal Crystal Growth, Structure, and Magnetic Properties of Ternary U(IV) Containing Fluorides: LiUF ₅ , KU ₂ F ₉ , K ₇ U ₆ F ₃₁ , RbUF ₅ , RbU ₂ F ₉ , and RbU ₃ F ₁₃ Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua Inorganic Chemistry, Vol. 53, Issue 12 https://doi.org/10.1021/ic5008507	journal	May 2014
Kinetics and mechanism of the disproportionation of uranium(V) Ekstrom, A. Inorganic Chemistry, Vol. 13, Issue 9 https://doi.org/10.1021/ic50139a035	journal	September 1974
Trivalent Cation-Controlled Phase Space of New U(IV) Fluorides, Na ₃ MU ₆ F ₃₀ (M = Al ³⁺ , Ga ³⁺ , Ti ³⁺ , V ³⁺ , Cr ³⁺ , Fe ³⁺ ): Mild Hydrothermal Synthesis Including an in Situ Reduction Step, Structures, Optical, and Magnetic Properties Yeon, Jeongho; Smith, Mark D.; Morrison, Gregory Inorganic Chemistry, Vol. 54, Issue 4 https://doi.org/10.1021/ic503034t	journal	January 2015
K ₃ (U ₃ O ₆ )(Si ₂ O ₇ ) and Rb ₃ (U ₃ O ₆ )(Ge ₂ O ₇ ): A Pentavalent-Uranium Silicate and Germanate Lin, Chia-Hui; Chen, Chih-Shan; Shiryaev, A. A. Inorganic Chemistry, Vol. 47, Issue 11 https://doi.org/10.1021/ic800300v	journal	June 2008
Ammonium Iron(II,III) Phosphate: Hydrothermal Synthesis and Characterization of NH₄Fe₂(PO₄)₂ Boudin, Sophie; Lii, Kwang-Hwa Inorganic Chemistry, Vol. 37, Issue 4 https://doi.org/10.1021/ic970655+	journal	January 1998
K(UO)Si ₂ O ₆ : A Pentavalent−Uranium Silicate Chen, Chih-Shan; Lee, Shang-Fan; Lii, Kwang-Hwa Journal of the American Chemical Society, Vol. 127, Issue 35 https://doi.org/10.1021/ja0543853	journal	September 2005
Application of a Mild Hydrothermal Approach Containing an in Situ Reduction Step to the Growth of Single Crystals of the Quaternary U(IV)-Containing Fluorides Na ₄ MU ₆ F ₃₀ (M = Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , and Zn ²⁺ ) Crystal Growth, Structures, and Magnetic Properties Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua Journal of the American Chemical Society, Vol. 136, Issue 10 https://doi.org/10.1021/ja412725r	journal	February 2014
Cs ₂ K(UO) ₂ Si ₄ O ₁₂ : A Mixed-Valence Uranium(IV,V) Silicate Lee, Cheng-Shiuan; Wang, Sue-Lein; Lii, Kwang-Hwa Journal of the American Chemical Society, Vol. 131, Issue 42 https://doi.org/10.1021/ja9071805	journal	October 2009
The Open Quantum Materials Database (OQMD): assessing the accuracy of DFT formation energies Kirklin, Scott; Saal, James E.; Meredig, Bryce npj Computational Materials, Vol. 1, Issue 1 https://doi.org/10.1038/npjcompumats.2015.10	journal	December 2015
Powder neutron diffraction study of potassium uranate(V), KUO3 Dickens, Peter G.; Powell, Anthony V. Journal of Materials Chemistry, Vol. 1, Issue 1 https://doi.org/10.1039/jm9910100137	journal	January 1991
Structure of USbO5: powder neutron diffraction study Dickens, Peter G.; Stuttard, Garry P. Journal of Materials Chemistry, Vol. 2, Issue 7 https://doi.org/10.1039/jm9920200691	journal	January 1992
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Synthèse et structure du borouranate de sodium, NaBUO5 Gasperin, M. Acta Crystallographica Section C Crystal Structure Communications, Vol. 44, Issue 3 https://doi.org/10.1107/S0108270187011405	journal	March 1988
Synthèse et structure du borouranate de lithium LiBUO5 Gasperin, M. Acta Crystallographica Section C Crystal Structure Communications, Vol. 46, Issue 3 https://doi.org/10.1107/S0108270189007948	journal	March 1990
Managing the Environmental Legacy of U.S. Nuclear-Weapons Production Crowley, Kevin; Ahearne, John American Scientist, Vol. 90, Issue 6 https://doi.org/10.1511/2002.6.514	journal	January 2002
A new low temperature route to uranyl borates with structural variations Wu, Shijun; Wang, Shuao; Polinski, Matthew J. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 228, Issue 9 https://doi.org/10.1524/zkri.2013.1616	journal	January 2013

Cited By (3)

Two-Dimensional Uranyl Borates: From Conventional to Extreme Synthetic Conditions: Two-Dimensional Uranyl Borates: From Conventional to Extreme Synthetic Conditions Hao, Yucheng; Kegler, Philip; Albrecht-Schmitt, Thomas E. European Journal of Inorganic Chemistry, Vol. 2020, Issue 4 https://doi.org/10.1002/ejic.201901239	journal	January 2020
Moderate supercritical synthesis as a facile route to mixed-valent uranium( iv , v ) and ( v , vi ) silicates Pace, Kristen A.; Klepov, Vladislav V.; Morrison, Gregory Chemical Communications, Vol. 54, Issue 98 https://doi.org/10.1039/c8cc07789d	journal	January 2018
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

Similar Records

Luminescence of alkali rare earth borates A₃Ln(BO₃)₂ (A = Na, K; Ln = Eu, Tb)

Journal Article · 2023 · Solid State Sciences · OSTI ID:2420553

Hines, Adrian T.; Morrison, Gregory; Yarbrough, Brandon J.; +3 more

Crystal structure of a new polar borate Na{sub 2}Ce{sub 2}[BO{sub 2}(OH)][BO{sub 3}]{sub 2} · H{sub 2}O with isolated boron triangles

Journal Article · 2016 · Crystallography Reports · OSTI ID:22645383

Topnikova, A. P.; Dimitrova, O. V.; Volkov, A. S.

Expanding the chemistry of borates with functional [BO₂]- anions

Journal Article · 2021 · Nature Communications · OSTI ID:1816184

Huang, Chunmei; Mutailipu, Miriding; Zhang, Fangfang; +6 more

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY

Title: Na2(UO2)(BO3): An All-Uranium(V) Borate Synthesized under Mild Hydrothermal Conditions

Citation Formats

References (39)

Cited By (3)

Linked Research (1)

Similar Records

Related Subjects

Title: Na₂(UO₂)(BO₃): An All-Uranium(V) Borate Synthesized under Mild Hydrothermal Conditions