Preparation, Structural Characterization, and Ion-Exchange Properties of Two New Zeolite-like 3D Frameworks Constructed by ε-Keggin-Type Polyoxometalates with Binding Metal Ions, H_11.4[ZnMo₁₂O₄₀Zn₂]^1.5– and H_7.5[Mn_0.2Mo₁₂O₄₀Mn₂]^2.1–

Abstract

Two new ε-Keggin-type polyoxometalate-based 3D frameworks, Na1.5H11.4[ε-Zn(II)Mo(V)10.9Mo(VI)1.1O40{Zn(II)}2] and (NH4)2.1H7.5[ε-Mn(II)0.2Mo(V)6Mo(VI)6O40{Mn(II)}2], are prepared, and their structures are determined by powder X-ray diffraction, Fourier transform infrared, Raman spectroscopy, and elemental analysis. ε-Keggin-type polyoxomolybdate units, [ε-ZnMo12O40] and [ε-Mn0.2Mo12O40], are linked with Zn(2+) and Mn(2+), respectively, in a tetrahedral fashion to form 3D frameworks. They show zeolite-like ion-exchange properties and redox properties. The ε-Keggin-based 3D framework shows high chemical composition diversity and can incorporate different elements in the framework.