三种新型乙酸功能化锆取代锗钨酸盐的合成、结构和电化学性质：从二聚体到四聚体。

Syntheses, Structures, and Electrochemical Properties of Three New Acetate-Functionalized Zirconium-Substituted Germanotungstates: From Dimer to Tetramer.

机构信息

MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering , Beijing Institute of Technology , Beijing 100081 , China.

出版信息

Inorg Chem. 2019 Feb 18;58(4):2372-2378. doi: 10.1021/acs.inorgchem.8b02805. Epub 2019 Jan 25.

DOI:10.1021/acs.inorgchem.8b02805

PMID:30680996

Abstract

Under hydrothermal conditions, three new acetate-functionalized zirconium-substituted polyoxometalates, HNa[Na(HO)][Zr(μ-O)(OH)(OAc)(α-GeWO)]·32HO (1), HKNa[Zr(μ-O)(OH)(OAc)(HO)(β-GeWO)]·20HO (2), HKNa[{Zr(μ-OH)(OH)}@{Zr(OAc)(α-GeWO)}]·22HO (3), were synthesized and characterized. In 1, the sandwiched dimer [Zr(μ-O)(OH)(OAc)(α-GeWO)] was linked to a hexameric [Na(HO)] cluster to form a 1D chain. In 2, the trimer was constructed from three [β-GeWO] units and a new [ZrO(OH)(OAc)(HO)] cluster. In 3, the tetramer was built by two novel sandwich-type dimers [Zr(OAc)(α-GeWO)] and one unique [Zr(μ-OH)(OH)] core in an approximately orthogonal fashion, showing a staggered tetrahedral polyanion. Also, the electrochemistry and electrocatalytic properties of 3 were studied, exhibiting good catalytic activities toward the reduction of HO, BrO, and NO.

摘要

在水热条件下，合成并表征了三种新的乙酸根功能化锆取代的多金属氧酸盐：HNa[Na(HO)][Zr(μ-O)(OH)(OAc)(α-GeWO)]·32HO（1）、HKNa[Zr(μ-O)(OH)(OAc)(HO)(β-GeWO)]·20HO（2）、HKNa[{Zr(μ-OH)(OH)}@{Zr(OAc)(α-GeWO)}]·22HO（3）。在 1 中，夹心二聚体[Zr(μ-O)(OH)(OAc)(α-GeWO)]与六聚体[Na(HO)]簇相连，形成 1D 链。在 2 中，三聚体由三个[β-GeWO]单元和一个新的[ZrO(OH)(OAc)(HO)]簇组成。在 3 中，四聚体由两个新型夹心型二聚体[Zr(OAc)(α-GeWO)]和一个独特的[Zr(μ-OH)(OH)]核以近似正交的方式构建，呈现交错的四面体形多阴离子。此外，还研究了 3 的电化学和电催化性能，表现出对 HO、BrO 和 NO 还原的良好催化活性。