Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Haijian Li; Philip Kegler; Vladislav V Klepov; Martina Klinkenberg; Dirk Bosbach; Evgeny V Alekseev

doi:10.1021/acs.inorgchem.8b01072

Comparison of Uranium(VI) and Thorium(IV) Silicates Synthesized via Mixed Fluxes Techniques

Inorg Chem. 2018 Jun 4;57(11):6734-6745. doi: 10.1021/acs.inorgchem.8b01072. Epub 2018 May 16.

Authors

Haijian Li^{1

2}, Philip Kegler¹, Vladislav V Klepov³, Martina Klinkenberg¹, Dirk Bosbach¹, Evgeny V Alekseev^{1

2}

Affiliations

¹ Institute of Energy and Climate Research (IEK-6) , Forschungszentrum Jülich GmbH , 52428 Jülich , Germany.
² Institut für Kristallographie , RWTH Aachen University , 52066 Aachen , Germany.
³ Samara National Research University , 443086 Samara , Russia.

PMID: 29767508
DOI: 10.1021/acs.inorgchem.8b01072

Abstract

Two uranium and two thorium silicates were obtained using high temperature mixed fluxes methods. K₁₄(UO₂)₃Si₁₀O₃₀ crystallizes in the P2₁/ c space group and contains open-branched sechser (six) single silicate chains, whereas K₂(UO₂)Si₂O₆ crystallizes in the C2/ c space group and is built of unbranched achter (eight) silicate chains. The crystals of K₁₄(UO₂)₃Si₁₀O₃₀ and K₂(UO₂)Si₂O₆ are related by increasing U/Si molar ratios, and both structures contain the same secondary building units (SBUs), [USi₆] heptamers. The triangle diagram for all known A⁺-UO₂²⁺-SiO₄^4- phases demonstrates the high polymerization level of silicate groups in the system, which was compared with the family of A⁺-UO₂²⁺-BO₃^3-/BO₄^5- compounds. For both thorium silicates, the transformation of K₂ThSi₂O₇ to K₂ThSi₃O₉ was found to be a factor of the reaction time. K₂ThSi₂O₇ crystallizes in the C2/ c space group and belongs to the Na₂Si^VISi₂O₇ structure type. Its 3D framework consists of diorthosilicate Si₂O₇ group and ThO₆ octahedra. Noncentrosymmetric K₂ThSi₃O₉ crystallizes in the hexagonal P6₃ space group and adopts mineral wadeite-type structure based upon triorthosilicate Si₃O₉ rings and ThO₆ octahedra. The coordination environment of thorium for all existing oxo-anion compounds including B, Si/Ge, P/As, Cr/Mo/W, and S/Se/Te are summarized and analyzed. Additionally, spectroscopic properties of all novel materials have been studied.