High-Temperature, High-Pressure Hydrothermal Synthesis and Characterization of a Salt-Inclusion Mixed-Valence Uranium(V,VI) Silicate: [Na9F2][(UVO2)(UVIO2)2(Si2O7)2]
journal contributionposted on 22.02.2016 by Yu-Chih Chang, Wen-Jung Chang, Sophie Boudin, Kwang-Hwa Lii
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A salt-inclusion mixed-valence uranium(V,VI) silicate, [Na9F2][(UVO2)(UVIO2)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: [Na9F2][(UVO2)(UVIO2)2(Si2O7)2], triclinic, P1̅ (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.