Zhang Zhiming, Qi Yanfei, Qin Chao, Li Yangguang, Wang Enbo, Wang Xinlong, Su Zhongmin, Xu Lin
Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Ren Min Street No. 5268, Changchun, Jilin 130024, PR China.
Inorg Chem. 2007 Oct 1;46(20):8162-9. doi: 10.1021/ic7012864. Epub 2007 Sep 6.
Two novel high-nuclear copper-substituted polyoxometalates, Na16[Cu14(OH)4(H2O)16(SiW8O31)4].20.5H2O (1) and K10Na14[Cu10(H2O)2(N3)4(GeW9O34)2(GeW8O31)2].30H2O (2), containing 14 Cu2+ ions and 10 Cu2+ ions, respectively, have been obtained in aqueous solution and characterized by IR, UV, TG, element analysis, electrochemistry, and single-crystal X-ray analyses. The polyoxoanion framework of 1 is composed of four [beta-SiW8O31] units connected by 14 Cu2+ ions to constitute a tetrameric compound. In 2, two [beta-GeW8O31] anions and two [B-alpha-GeW9O34] anions are connected together by a [Cu10(N3)4O32(H2O)2] {Cu10(N3)4} cluster to construct a novel tetrameric compound. The results of the electrocatalytic experiments reveal that the reduced species of 1 and 2 have electrocatalytic activities for nitrate reduction.
已在水溶液中制得两种新型的高核铜取代多金属氧酸盐，即Na16[Cu14(OH)4(H2O)16(SiW8O31)4].20.5H2O (1) 和K10Na14[Cu10(H2O)2(N3)4(GeW9O34)2(GeW8O31)2].30H2O (2)，它们分别含有14个Cu2+离子和10个Cu2+离子，并通过红外光谱、紫外光谱、热重分析、元素分析、电化学以及单晶X射线分析对其进行了表征。1的多金属氧阴离子骨架由四个[β-SiW8O31]单元通过14个Cu2+离子连接而成，构成一种四聚体化合物。在2中，两个[β-GeW8O31]阴离子和两个[B-α-GeW9O34]阴离子通过一个[Cu10(N3)4O32(H2O)2] {Cu10(N3)4}簇连接在一起，构建成一种新型的四聚体化合物。电催化实验结果表明，1和2的还原物种对硝酸盐还原具有电催化活性。
