三核和四核金属-有机簇修饰的四个多酸化合物的结构、选择性光催化和汞离子传感性能  

Four Keggin Compounds Modified by Tri⁃and Tetra⁃nuclear Metal⁃Organic Clusters:Structures,Selective Photocatalytic and Hg2+Recognition Characteristics

作　　者：应俊[1] 张宝月 田爱香[1] YING Jun;ZHANG Bao-Yue;TIAN Ai-Xiang(Department of Chemistry,Bohai University,Jinzhou,Liaoning 121013,China)

机构地区：[1]渤海大学化学系,锦州121013

出　　处：《无机化学学报》2020年第10期1831-1844,共14页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21571023,21101015);辽宁省兴辽英才青年拔尖项目(No.XLYC1807049);辽宁省教育厅项目(No.LQ2020010、LJ2019006)资助。

摘　　要：使用柔性含S有机配体4-(2-噻吩-2-基-乙基)-4H-[1,2,4]三氮唑(L),通过调控反应参数成功制备出4个基于Keggin的化合物,即[CuⅠ3L3(PMo12O40)](1)、[CuⅠ4L6(SiW12O40)](2)、[CuⅠ4L6(SiMo12O40)](3)和[Zn4L6(SiW12O40)](4),并利用单晶X射线衍射、元素分析和红外光谱进行表征。化合物1中3个Cu+离子聚合3个配体诱导一个环状的三核铜簇。Keggin多阴离子连接三核簇构筑二维层结构。化合物2、3和4同构,包含由6个配体连接4个金属离子(2、3中为铜离子,4中为锌离子)形成的四核[M4L6]4+簇。多酸阴离子提供2个氧原子连接2个[M4L6]4+簇,从而形成一维链结构。标题化合物对废水中的阳离子染料亚甲基蓝(MB)展示了良好的选择性光催化性能。另外2-CPE(碳糊电极)可作为安培传感器来检测过氧化氢和亚硝酸根。化合物1、2和4展示了对Hg2+的传感性能。By using a flexible S-containing ligand 4-(2-thiophen-2-yl-ethyl)-4H-[1,2,4]triazole(L),four Kegginbased compounds,namely[CuⅠ3L3(PMo12O40)](1),[CuⅠ4L6(SiW12O40)](2),[CuⅠ4L6(SiMo12O40)](3)and[Zn4L6(SiW12O40)](4),were successfully synthesized by controlling the reaction parameters and well characterized by single-crystal X-ray diffraction,elemental analyses,and IR spectra.In compound 1,three Cu+ions are fused by three L ligands inducing a cyclic tri-nuclear Cu+cluster.The Keggin anions link the tri-nuclear clusters to construct a 2D layer.Compounds 2,3 and 4 are isostructural,including a tetra-nuclear[M4L6]4+cluster with six L ligands connected by four M ions(M=Cu in 2 and 3,Zn in 4).The Keggin anion offers two O atoms to link two[Cu4L6]4+clusters and a 1D chain is formed.The title compounds exhibited good selective degradation of cationic methylene blue(MB)dye in wastewater.Additionally,the 2-CPE(carbon paste electrodes)could act as an amperometric sensor for detection of hydrogen peroxide and nitrite.Compounds 1,2 and 4 also showed Hg2+recognition properties.CCDC:1879845,1;1879846,2;1879847,3;1895379,4.

关 键 词：多酸基化合物 电化学性能 选择性光催化 Hg2+传感 

分 类 号：O614.121[理学—无机化学] O614.241[理学—化学]