Reaction in the system N(CH3)4-ZrO2-P2O5-H2O. Preparation and characterization of framework zirconium phosphates (NH4)xH1-xZr2(PO4)3 and HZr2(PO4)3.

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概要

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• The hydrothermal reaction in the system ZrO<SUB>2</SUB>–P<SUB>2</SUB>O<SUB>5</SUB>–H<SUB>2</SUB>O in the presence of tetramethylammonium ions was examined within the temperature range 160–350 °C. This reaction resulted in the formation of framework zirconium phosphates (NH<SUB>4</SUB>)<I><SUB>x</SUB></I>H<SUB>1−<I>x</I></SUB>Zr<SUB>2</SUB>(PO<SUB>4</SUB>)<SUB>3</SUB>·<I>y</I>H<SUB>2</SUB>O (0.6≤<I>x</I>≤1,<I>y</I>≤0.3) as well as some other phases, including two tetramethylammonium intercalates. The framework phases were rhombohedral with lattice constants of, <I>e.g.</I>, <I>a</I>=8.669 and <I>c</I>=24.23 Å for <I>x</I>=1.0. These phases were deammonated at 400–640 °C and converted to the proton-exchanged form HZr<SUB>2</SUB>(PO<SUB>4</SUB>)<SUB>3</SUB>. The protons of this phase are easily exchanged by unhydrated Li<SUP>+</SUP> and Na<SUP>+</SUP> ions, but not by K<SUP>+</SUP> and Cs<SUP>+</SUP>, owing to the sieving effect of the bottleneck in the (Zr<SUB>2</SUB>P<SUB>3</SUB>O<SUB>12</SUB>)<SUP>−1</SUP> framework. The acid strength of the proton form is a little weaker than that of α-zirconium phosphate.

• 公益社団法人 日本化学会の論文

著者

• KIJIMA Tsuyoshi

  National Institute for Research in Inorganic Materials

• YAJIMA Yoshiyuki

  National Institute for Materials Science, Advanced Materials Laboratory

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