【摘要】 室温下以4-(3-吡啶基)-2-巯基咪唑(PyimsH)和Cu(ClO4)2.6H2O为原料,在甲醇介质中制备了四核铜簇合物单晶[Cu4(Pyims)4].4H2O.4CH3OH。该簇合物属四方晶系,I41/a空间群。4个亚铜中心离子构成1个变形四面体,4个Pyims-配体以咪唑环上的N原子和巯基上的S原子与亚铜离子配位,其中S原子以桥基形式同时与2个亚铜离子配位。相邻簇合物分子通过配体Pyims-吡啶环上N3及C7之间的氢键交互作用,构筑成三维网状结构。采用简单的滴涂法将该簇合物修饰于玻碳电极表面,簇合物对O2气还原有良好的电催化活性,具有作为燃料电池电极材料的潜质。更多还原

【Abstract】 A tetranuclear cluster crystal [Cu4(Pyims)4]·4H2O·4CH3OH was synthesized from the reaction between cupric perchlorate and 4-(3-pyridyl)-2-mercapto imidazole(PyimsH) in methanol medium at room temperature,and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The results reveal that the compound belongs to tetragonal system with space group I41/a.The cell parameters are a=1.44432(12) nm,b=1.44432(12) nm,c=2.2119(3) nm,α=90°,β=90°,γ=90°,V=4.6142(8) nm3,Z=4,Dc=1.669 Mg/m3,Mr=1159.26,R1=0.0761,wR2=0.1839(I>2σ).In the cluster molecule,the Cu4+4 core takes a distorted tetrahedron configuration.Four Pyims-ligands coordinate with cuprous ions by N atom of imidazole and S atom of sulfhydryl,and two cuprous ions are linked by one S atom t.The cluster molecules are held together via the N(3)H(7)C(7) hydrogen-bondings,which result in a three-dimensional network geometry.The electrochemical behavior of the title cluster was studied by cyclic voltammetry.Through simple dropcoating method,the title cluster was used to modify the surface of glassy carbon electrode(GCE) to fabricate an amperometric sensor.It has been found that the peak potential of the oxygen reduction at the modified electrode is positively shifted from-0.55 V to-0.247 V in pH=5.9 phosphate buffer solution.The obvious decrease of the over potential indicates that the sensor has high electrocatalytic activity to oxygen reduction,which suggests that the title cluster complex can be used as the anode material for fuel cells.更多还原