四核铜簇合物[Cu_4(Pyims))4]·4H_2O·4CH_3OH的合成、晶体结构及电催化性能  

Synthesis,Crystal Structure and Electrocatalytic Properties of a Tetranuclear Copper Cluster Complex [Cu_4(Pyims)_4]·4H_2O·4CH_3OH

作　　者：王明艳[1,2] 许兴友[2,3] 马卫兴[2] 曹志凌[2] 杨绪杰[1] 

机构地区：[1]南京理工大学化工学院 [2]淮海工学院化学工程学院,连云港222005 [3]淮阴工学院,淮阴223003

出　　处：《应用化学》2011年第3期290-296,共7页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(50873042);江苏省海洋资源开发研究院科技开放基金(JSIMR09B05);江苏省自然科学基金(BK2009651)资助项目

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。A tetranuclear cluster crystal [ Cu4 （Pyims） 4 ] ·H2O·4CH3 OH 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. A,A,A,32（12） nm, b = 1. n,A,A,32（12） nm, c =2.2119（3） nm,α=90°, β=90°, y =90°, V=4.6142（8） nm3, Z=4, Do =1.669 Mg./m3, Mr =1159.26, R1 =0.0761, wR2 =0. 1839（I 〉2σ）. In the cluster molecule, the Cu4＋ core takes a distorted tetrahedron configuration. Four Pyimsligands 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 threedimensional network geometry. The electrochemical behavior of the title cluster was studied by cyclic vohammetry. 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.

关 键 词：铜簇合物 合成 晶体结构 电催化 氧气 

分 类 号：O641[理学—物理化学]