skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth

Journal Article · · Frontiers in Chemistry
; ; ;

We report single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs11[(UO2)12(PO4)3O13] (1) and Rb11[UO2)12(PO4)3O12F2] (2) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U3O8, while Cs4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (3) and Rb4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (4) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2-4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase (1) and in contrast an oxyfluoride phase for the Rb containing phase (2). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the UO 2 2 + uranyl group.

Research Organization:
Univ. of South Carolina, Columbia, SC (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Hierarchical Waste Form Materials (CHWM)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF)
Grant/Contract Number:
SC0016574; 1250052
OSTI ID:
1564451
Alternate ID(s):
OSTI ID: 1612658
Journal Information:
Frontiers in Chemistry, Journal Name: Frontiers in Chemistry Vol. 7; ISSN 2296-2646
Publisher:
Frontiers Research FoundationCopyright Statement
Country of Publication:
Switzerland
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (31)

Generalized Gradient Approximation Made Simple journal October 1996
Structure validation in chemical crystallography journal January 2009
Projector augmented-wave method journal December 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Observation of an Unusual Uranyl Cation–Cation Interaction in the Strongly Fluorescent Layered Uranyl Phosphates Rb 6 [(UO 2 ) 7 O 4 (PO 4 ) 4 ] and Cs 6 [(UO 2 ) 7 O 4 (PO 4 ) 4 ] journal December 2017
Hierarchical Materials as Tailored Nuclear Waste Forms: A Perspective journal June 2018
Recent spectroscopic studies of UO2 journal January 1987
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Ca 2 SiO 3 OHF—A high-pressure phase with dense calcium polyhedral packing and tetrahedral silicon journal January 2005
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Flux crystal growth: a versatile technique to reveal the crystal chemistry of complex uranium oxides journal January 2019
Crystal structure refinement with SHELXL journal January 2015
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators journal August 1995
A 5 RE 4 X[TO 4 ] 4 crystal growth and photoluminescence. Fluoride flux synthesis of sodium and potassium rare earth silicate oxyfluorides journal January 2015
Bond lengths in oxygen and halogen compounds of d and f elements journal November 1978
Crystal Growth and Structure Characterization of Three Layered Uranyl Phosphates and Their Relation to the Phosphuranylite Family journal December 2018
Systematic Analysis of Core Photoemission Spectra for Actinide Di-Oxides and Rare-Earth Sesqui-Oxides journal January 1992
Understanding the Formation of Salt-Inclusion Phases: An Enhanced Flux Growth Method for the Targeted Synthesis of Salt-Inclusion Cesium Halide Uranyl Silicates journal May 2016
Crystal growth and structure of three new neodymium containing silicates: Na0.50Nd4.50(SiO4)3O, Na0.63Nd4.37(SiO4)3O0.74F0.26 and Na4.74Nd4.26(O0.52F0.48)[SiO4]4 journal September 2014
The Crystal Structure of Bergenite, a new Geometrical Isomer of the Phosphuranylite Group journal February 2003
Density-functional theory and NiO photoemission spectra journal December 1993
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 ) 3 O 2 (PO 4 ) 2 ] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange journal March 2018
Crystal growth, structural characterization, cation–cation interaction classification, and optical properties of uranium( vi ) containing oxychlorides, A 4 U 5 O 16 Cl 2 (A = K, Rb), Cs 5 U 7 O 22 Cl 3 , and AUO 3 Cl (A = Rb, Cs) journal January 2014
The importance of accurate crystal structure determination of uranium minerals. I. Phosphuranylite KCa(H3O)3(UO2)7(PO4)4O4.8H2O journal August 1991
Materials Discovery by Flux Crystal Growth: Quaternary and Higher Order Oxides journal January 2012
PF6− Hydrolysis as a route to unique uranium phosphate materials journal January 2008
Overstepping Löwenstein’s Rule—A Route to Unique Aluminophosphate Frameworks with Three-Dimensional Salt-Inclusion and Ion-Exchange Properties journal December 2018
A Revised and Expanded Structure Hierarchy of Natural and Synthetic Hexavalent Uranium Compounds journal January 2016
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Mild Periodic Acid Flux and Hydrothermal Methods for the Synthesis of Crystalline f-Element-Bearing Iodate Compounds journal October 2017
Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database journal August 1985

Similar Records

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
Journal Article · Mon Apr 02 00:00:00 EDT 2018 · Inorganic Chemistry · OSTI ID:1564451
+2 more
Understanding the Polymorphism of A4[(UO2)3(PO4 )2O2] (A = Alkali Metals) Uranyl Phosphate Framework Structures
Journal Article · Thu Dec 13 00:00:00 EST 2018 · Crystal Growth and Design · OSTI ID:1564451
+2 more
Molten salt flux synthesis and crystal structure of a new open-framework uranyl phosphate Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}: Spectroscopic characterization and cationic mobility studies
Journal Article · Mon Apr 15 00:00:00 EDT 2013 · Journal of Solid State Chemistry · OSTI ID:1564451

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemistry
flux crystal growth
uranyl
phosphuranylite
single crystal
DFT