研究进展

牛景杨教授课题组:Chem. Eur. J.,2016, 22(31), 10983-10989.

信息来源: 暂无 发布日期: 2016-06-27浏览次数:

题 目:  Unprecedented {Fe14}/{Fe10} Polyoxotungstate-Based Nanoclusters with Efficient Photocatalytic H2 Evolution Activity: Synthesis, Structure, Magnetism, and Electrochemistry

:  Vikram Singh, Zhiyuan Chen, Pengtao Ma, Dongdi Zhang, Michael G. B. Drew, Jingyang Niu*, Jingping Wang*

:  Chem. Eur. J

年卷页:  2016, 22(31), 10983-10989

要:Novel Fe10 and Fe14 clusters [Rb9Cs4H37Fe10O34(A-a-PW9O31)3(OH)3]·36H2O (1) and [H3Rb3Fe14(OH)12(PO4)6(B-a-PW9O34)2]·21H2O (2) were synthesized and characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), and magnetic studies, and in solution by electrochemistry. Cluster 1 is a decameric FeIII polyanionic cluster encapsulating a cesium atom in the center. Cluster 2 is a unique tetradecanuclear FeIII sandwich structure with phosphate-linked units featuring two quasicubic Fe4O4 moieties. Apparently, 2 has the highest nuclearity of all known FeIII sandwich-type polyoxometalate clusters. Clusters 1 and 2 also act as photocatalysts with platinum as cocatalyst for H2 evolution from light-driven water splitting. Changes in the cyclovoltammetric patterns  with variations in pH were observed for 1 and 2, most likely due to intermolecular interactions among the high-nuclearity FeIII cluster cores and subsequent changes in the acid-base properties of the two reduced POMs. Magnetic studies provide evidence of antiferromagnetic interactions in 1 and 2. TGA showed that complexes 1 and 2 decompose between 580 and 590℃.