Series-Functional Ion Exchange. 1-4. Manganese Oxide Ion-Sieves. (4). Application as a Selective Recognition and Response Material.
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Ion-sieve crystals have pores narrower than the conventional porous materials. They are expected to use as selective recognition and response materials for certain metal ions. The applicabilities of ion-sieve crystals to an adsorbent for lithium isotope separation, an electrochemical adsorbent, an electrochromic material, a cathode material for secondary lithium battery, and a lithium ion-selective electrode were investigated mainly with manganese oxide ion sieves. Cubic antimonic acid, which shows a high selectivity for sodium ions, gives the highest separation factor for lithium isotopes. The difference in the separation factors with ion-sieve crystals could be well explained by considering two factors: the difference in hydration circumstances of lithium ions between the exchanger and the solution phase, and the influence of lithium ion stabilization in the solid phase. The electrochemical Li<SUP>+</SUP> insertion into a Pt/spinel-type-manganese-oxide (λ-MnO<SUB>2</SUB>) electrode took place effectively in LiCl solution with concentration higher than 10 mM. The lithium uptake reached 11 mg/g-MnO<SUB>2</SUB> by the electrochemical treatment of geothermal water with this electrode. A reversible change in visible light absorbance at about 450 nm occurred with the Li<SUP>+</SUP> insertion/extraction on NESA/λ-MnO<SUB>2</SUB> electrode. Cyclic voltammetry indicated that the absorbance change couples with the electrochemical response of the manganese oxide to Li<SUP>+</SUP> ions. A hollandite-type manganese oxide, without foreign cations in the [2×2] tunnel, was prepared directly by reacting LiMnO<SUB>4</SUB> and Mn (NO<SUB>3</SUB>) <SUB>2</SUB> in an acidic solution. A preliminary electrochemical study suggested that the hollandite type manganese oxide is promising as the cathode for a lithium rechargeable battery. A Pt/λ-MnO<SUB>2</SUB> electrode shows a highly selective response to Li<SUP>+</SUP> even in a solution containing large amounts of Na<SUP>+</SUP> and K<SUP>+</SUP> This is expected to be a good lithium ion-selective electrode, especially needed in the field of clinical chemistry.
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