High-temperature, high-pressure hydrothermal synthesis and characterization of a salt-inclusion mixed-valence uranium(V,VI) silicate: [Na9F 2][(UVO2)(UVIO2) 2(Si2O7)2]

Yu Chih Chang, Wen Jung Chang, Sophie Boudin, Kwang Hwa Lii

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Abstract

A salt-inclusion mixed-valence uranium(V,VI) silicate, [Na 9F2][(UVO2)(UVIO 2)2(Si2O7)2], was synthesized under hydrothermal conditions at 585 C and 160 MPa and structurally characterized by powder and single-crystal X-ray diffraction (XRD). The valence states of uranium were established by U 4f X-ray photoelectron spectroscopy (XPS). The structure contains two-dimensional (2D) sheets of uranyl disilicate with the composition [UO2Si2O7], which are connected by U(1)VO6 tetragonal bipyramids to form thick layers. The Na+ cations are located at sites in the intralayer and interlayer regions. In addition to Na+ cations, the interlayer region also contains F- anions such that infinite chains with the formula FNa1/1Na4/2 are formed. The same type of chain was observed in K2SnO3. The title compound is not only the first example of salt-inclusion metal silicate synthesized under high-temperature, high-pressure hydrothermal conditions, as well as the first salt-inclusion mixed-valence uranium silicate, but it is also the first mixed-valence uranium(V,VI) silicate in the literature. Crystal data: [Na 9F2][(UVO2)(UVIO 2)2(Si2O7)2], triclinic, P1̄ (No. 2), a = 5.789(1) Å, b = 7.423(2) Å, c = 12.092(2) Å, α = 90.75(3), β = 96.09(3), γ = 90.90(3), V = 516.5(2) Å3, Z = 1, R1 = 0.0241, and wR2 = 0.0612.

Original languageEnglish
Pages (from-to)7230-7235
Number of pages6
JournalInorganic Chemistry
Volume52
Issue number12
DOIs
StatePublished - 17 Jun 2013

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