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Mild Periodic Acid Flux and Hydrothermal Methods for the Synthesis of Crystalline f-Element-Bearing Iodate Compounds

日期:2017-10-8 15:02:50 人气:12 

Abstract

f-element-bearing iodate compounds are a large family mostly synthesized by hydrothermal reactions starting with actinide/lanthanide ions and  iodic acid or iodate salt. In this work, we introduce melting periodic acid flux as a reaction medium and provide a safe way for single-crystal growth of a series of new f-element iodate compounds including UO2(IO3)2·H2O (1), UO2(IO3)2(H2O)· 18 HIO3 (2), α-Th(IO3)2(NO3)(OH) (3), β-Th(IO3)2(NO3)(OH) (4), and

(H3O)9Nd9(IO3)36·3HIO3 (5). The structures of these compounds deviate from those afforded from hydrothermal reactions. Specifically, compounds 1 and 2 exhibit pillared structures consisting of uranyl pentagonal bipyramids and iodate trigonal pyramids. Compounds 3 and 4 represent two new thorium iodate compounds that are constructed from subunits of thorium dimers. Compound 5 exhibits a flower shaped trivalent lanthanide iodate structure with HIO3 molecules and H3O+ cations filled in the channels. The aliovalent replacement of f-elements in 5 is available from a hydrothermal process, further generating compounds of Th2(IO3)8(H2O) (6) and Ce2(IO3)8(H2O) (7). The distinct absorption features are observed in isotypic compounds 5−7, where 7 shows typical semiconductor behavior with a band gap of 2.43 eV. Remarkably, noncentrosymmetric 1, 6, and 7 exhibit strong second-harmonic-generation efficiencies of 1.3, 3.2, and 9.2 times, respectively, that of the commercial material KH2PO4. Additionally, the temperature-dependent emission spectra of 1 and 2 were also collected showing typical emission features of uranyl units and a negative correlation between the intensities of the emissions with temperature. Clearly, the presented low-temperature melting inorganic acid flux synthesis would provide a facile and effective strategy to produce a large new family of structurally versatile and multifunctional f-element inorganic compounds.