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Different from the conventional synthesis approaches, such as hydrothermal or solvothermal synthesis, a porous metal azolate framework encapsulating Keggin-type [SiW12 O40 ](4-) anions was prepared by an environmentally friendly, low-cost, and highly efficient steam-assisted conversion method for the first time. The nanosized polyoxometalates as a template were encapsulated by a zeotype 6(4) 4(8) cage constructed by 28 nuclear zinc atoms connected through 32 Trz ligands. The obtained composite exhibits excellent thermal and chemical stability; meanwhile, its special ability to selectively absorb water from alcohols makes it efficiently separate water from analytically pure ethanol, with the result that water content decreases from 0.23 to 0.05 wt %, which is superior to the standard of chromatographic grade ethanol (<0.1 wt %). Besides, alternating current (ac) impedance experiments also reveal that the hybrid is a kind of proton conductive material., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A stable metal-organic framework pillared by Keggin-type polyoxometalate, Cu6 (Trz)10 (H2O)4 [H2 SiW12 O40 ]⋅8 H2O (Trz=1,2,4-triazole) (1), has been prepared under hydrothermal condition. The 2D layer structure with a 22-member ring was formed by Cu(2+) ions, which are connected with each other via the Trz ligands on the ab plane. Thus, the 2D layers are further interconnected through Keggin polyoxoanions to generate a 3D porous network with a small 1D channel. Moreover, the presence of polyoxoanions make it exhibit selective adsorption of water and proton-conducting properties. Additionally it showed efficient intrinsic peroxidase-like activity, providing a simple and sensitive colorimetric assay to detect H2O2 ., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)