A Trinuclear Zr-Substituted Decanuclear Hetero-Metal Sandwich Tungstoantimonate: Synthesis, Structure and Properties

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

来源：European Journal of Inorganic Chemistry, 2019, 3-4: 486-491.

DOI：10.1002/ejic.201800546

• Polyoxotungstates
• Trilacunary
• Sandwich complexes
• Electrochemistry
• Electrocatalytic performances

A new trinuclear Zr4+ cluster substituted decanuclear hetero-metal sandwich tungstoantimonate aggregate [H2N(CH3)(2)](7)Na3H5{[Zr-3(OAc)W-7(H2O)O-25][B-alpha-SbW9O33](2)}center dot 22H(2)O (1) has been synthesized under hydrothermal condition by reacting [B-alpha-SbW9O33](9-) precursor, ZrOCl2 center dot 8H(2)O, Na2WO4 center dot 2H(2)O and dimethylamine hydrochloride in sodium acetate buffer (pH = 4.8) and structurally characterized by elemental analyses, IR spectrum, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The structure unit of 1 consists of a new sandwich tungstoantimonate (TA) unit {[Zr-3(OAc)W-7(H2O)O-25][B-alpha-SbW9O33](2)}(15-) constituted by two trivacant Keggin [B-alpha-SbW9O33](9-) fragments linked through an unseen hetero-metal cluster [Zr-3(OAc)W-7(H2O)O-25](3+). In addition, the polyoxoanion can also be described as two trivacant Keggin [B-alpha-SbW9O33](9-) fragments and one divacant Lindqvist [W4O16](8-) linked by a hexanuclear hetero-metal cluster [Zr-3(OAc)W-3(H2O)O-9](11+) link. Moreover, the solid-state electrochemistry and electrocatalytic performances of 1 have been measured in 0.5 mol L-1 Na2SO4 + H2SO4 aqueous solution, and the results show that 1 illustrates comparatively apparent catalytic activities toward the BrO3- and H2O2 reduction.

• 出版日期2019-1-31
• 单位北京理工大学