钴（四氮杂环十四）络合物的结构对其电化学及电催化性质的影响

The Effects of the structure of Co (Ⅲ) - (Tetraazacyclotetradeca) Complexes on Their Electrochemical Behavior and Catalyric Properties

本文选择了３种具有不同配体结构的钴（四氖杂环十四）络合物：ＣＯ（Ⅲ）Ｃｙｃｌａｍ（１．４，８，１１－四氮杂环十四烷），ＣＯ（Ⅲ）－ＤＩＭ（２，３－二申基。１，４，８，１１－四氮杂环。（１，３）－二烯）和Ｃｏ（Ⅲ）－ＴＩＭ（２．３，９，１０－四甲基－１，４，８，１１－四氮杂环。［１，３．８，１０］－四烯）．研究平面配体（Ｎ４）结构的变化．主要是氮杂环不饱和程度的变化对３种络合物在酸性及中性溶液中电化学行为的影响，以及３种络合物在中性溶液中对还原的电催化活性。研究表明，随络合物中组杂环不饱和程度的增加．其配位场强度增强，络合物的自还原电位均向正的方向移动。大小顺序为：Ｃｏ（Ⅲ）－Ｃｙｃｌａｍ＜Ｃｏ（Ⅲ）－ＤＩＭ＜Ｃｏ（Ⅲ）－ＴＩＭ，而对还原的电催化活性则以Ｃｏ（Ⅲ）－Ｃｙｃｌａｍ最强，ＣＯ（Ⅲ）－ＤＩＭ次之，Ｃｏ（Ⅲ）－ＴＩＭ无明显的电催化活性。

The effects of structural changes of Co (Ⅲ)-(tetraazacyclotetradeca) complexes on their electrochemical behavior in acid and neutral solutions and on their electrocatalyric characteristics for NO3 reduction in neutral solution are studies. In this paper three Co (Ⅲ)- (tetraazacyclotetradeca), Co (Ⅲ) 3-DIM (2, 3, 9, 10-tetramethyl-1, 4, 8, 11-tetraazacyclotetradeca-1 , 3, 8, 10-tetrene) were studied. The Results indicate that with the increase in the number of C=N bonds in complexes, the ligand field strengthens becomes stronger, and the half-wave potentials of Co-Couplexes shift toward the positive directions in the order of Co (Ⅲ) -TIM>Co (Ⅲ) -DIM>Co (Ⅲ) -cvclam, but the electrocatalytic activities for NO3 reduction change in the opposite way.