New development of inorganic ion exchanger: High Cs+ Selective Sodium Difluorotetrasilicic Mica-A NMR Approach-:—A NMR Approach—
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概要
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Sodium difluorotetrasilicic mica (Na [Mg<SUB>2.5</SUB>Si<SUB>4</SUB>O<SUB>10</SUB>F<SUB>2</SUB>] ⋅<I>n</I>H<SUB>2</SUB>O; Na-TSM) had the highest ion-exchange selectivity for Cs<SUP>+</SUP> among alkali metal ions in spite of its large crystallographic ionic radius, because of its unusual cesium ion-exchange reaction with magnesium ions that were a lattice component of Na-TSM in addition to the ordinary ion-exchange reaction with Na<SUP>+</SUP>. To elucidate the phenomenon, <SUP>23</SUP>Na, and <SUP>133</SUP>Cs solid NMR were applied to examine the role of Na<SUP>+</SUP> and Cs<SUP>+</SUP> in Na-TSM layer where the Na<SUP>+</SUP> /Cs<SUP>+</SUP> ion-exchange reaction participates. The observed NMR spectra of <SUP>23</SUP>Na and <SUP>133</SUP>Cs indicated rather restricted motion of these ions and molecule. The result signified that Na<SUP>+</SUP> and Cs<SUP>+</SUP> were buried in the hexagonal cavities of basal oxygen planes of mica rather than in the interlayer space of layered gallery. When Cs<SUP>+</SUP> was ion-exchanged with Mg<SUP>2+</SUP> located in the skeleton of Na-TSM, Cs<SUP>+</SUP> was strongly sorbed into this site to keep the charge balance. These findings were well accounted for the unique hydration property of alkali metal ions that has been specified in liquid water such as hydrated ionic radii.
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