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The Keggin-type polyoxometalates (POMs) are effective catalysts for oxidative desulfurization (ODS) and confining these POMs in metal-organic frameworks (MOFs) is a promising strategy to improve their performances. Herein, postsynthetic modification of POMs confined in MOFs by adding thiourea creates more unsaturated metal sites as defects, promoting ODS catalytic activity. Additional modification by confining 1-butyl-3-methyl imidazolium POMs in MOFs is performed to obtain higher ODS activity, owing to the affinity between electron-rich thiophene-based compounds and electrophilic imidazolium compounds. The ODS catalytic activities of four Zr-MOF-based composites (bottle around ship) including phosphomolybdate acid (PMA)/UiO-66, [Bmim]3 PMo12 O40 /UiO-66, PMA/Thiourea/UiO-66, and [Bmim]3 PMo12 O40 /Thiourea/UiO-66 are therefore investigated in detail. In order to explore the catalytic mechanism of these MOF composites, their microstructures and electronic structures are probed by various techniques such as X-ray diffraction, thermogravimetric analysis, Fourier transform infrared, Raman, scanning electron microscope, transmission electron microscope, BET, X-ray photoelectron spectroscopy, EPR, UV-vis, NMR spectra, and H2 -temperature-programmed reduction. The results reveal that phosphomolybdate blues and imidazolium phosphomolybdate blues with different Mo5+ /Mo6+ ratios with the Keggin structure are confined in defected UiO-66 for all four composites. This approach can be applied to design and synthesize other POMs/MOFs composites as efficient catalysts.

Two high porous thioindates with 1,6-diaminohexane (DAH), DAH-InS-1 and DAH-InS-2, were prepared by solvothermal reaction. Though the same T3 supertetrahedral frameworks were reported, the cations are different. DAH is a non-cyclic diamine and also an economical reagent for synthesis. Because of the structural difference of the structural directing agents, the dimensions of crystal cells of DAH-InS-1 and DAH-InS-2 are elongated and the total volumes for the cation and solvent are 74.6 and 72.1 % (Platon) larger relative to those reported previously. The two compounds were obtained in one reaction system by controlling the reaction time. Their structures are briefly discussed and the correlativity of crystal shape with the parameters of microstructure is discussed.

Tn clusters are usually connected into frameworks by sulfur bridges. A new type of T4 compounds in which the clusters are linked by both sulfur bridges and transition metal complexes are described.

Two high porous thioindates with 1,6-diaminohexane (DAH), DAH-InS-1 and DAH-InS-2, were prepared by solvothermal reaction. Though the same T3 supertetrahedral frameworks were reported, the cations are different. DAH is a non-cyclic diamine and also an economical reagent for synthesis. Because of the structural difference of the structural directing agents, the dimensions of crystal cells of DAH-InS-1 and DAH-InS-2 are elongated and the total volumes for the cation and solvent are 74.6 and 72.1 % (Platon) larger relative to those reported previously. The two compounds were obtained in one reaction system by controlling the reaction time. Their structures are briefly discussed and the correlativity of crystal shape with the parameters of microstructure is discussed.