A new tetra-Zr(iv)-substituted polyoxotungstate aggregate

作者：Li, Hai-Lou; Wang, Yue-Lin; Zhang, Zhong; Yang, Bai-Feng; Yang, Guo-Yu^*

来源：Dalton Transactions, 2018, 47(39): 14017-14024.

DOI：10.1039/c8dt03317j

• TRANSITION-METAL CLUSTERS
• HYDROTHERMAL CONDITIONS
• ORGANIC FRAMEWORKS
• CRYSTAL-STRUCTURE
• NITRIC-OXIDE
• POLYOXOMETALATE
• COMBINATION
• CENTERS
• REDUCTION
• CHEMISTRY

A new tetra-Zr-substituted tungstophosphate (TP), [H2N(CH3)(2)](6)Na6H8{Zr-2[SbP2W4(OH)(2)O-21][alpha(2)-PW10O38]}(2)center dot 50H(2)O (1), has been made by the hydrothermal reaction of the [B--SbW9O33](9-) building block with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and NaOAc-HOAc (pH = 4.8), and further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), P-31 NMR spectroscopy and single-crystal X-ray diffraction. 1 is a toroidal structure formed by two divacant [alpha(2)-PW10O38](11-) units and two [SbP2W4(OH)(2)O-21](7-) fragments linked by four Zr4+ cations. Note that the TP is reassembled with tetrahedral PO4 replacing the triangular pyramidal SbO3 in the [B-alpha-SbW9O33](9-) precursor. In addition, the pendant SbO3 derives from the dissociation of the [B-alpha-SbW9O33](9-) precursor. Furthermore, the electrochemical properties of 1 have been studied in Na2SO4 + H2SO4 supporting electrolyte (0.5 mol L-1), and indicate that 1 exhibits apparent catalytic activity toward H2O2 and BrO3- reduction. The P-31 NMR spectrum of 1 exhibits three signals with approximately proportional intensities, which is consistent with the solid-state structure.

• 出版日期2018-10-21
• 单位北京理工大学