meso-四(4-N-甲基吡啶基)卟啉-金属-氧簇超分子化合物的光谱及电催化氧还原行为研究  

Spectral and Electrocatalyticly Reducing Dioxygen of meso-Tetrakis(4-N-methylpyridy)porphyrin-Metal-Oxo Cluster Supramolecular Complex

作　　者：刘淑清[1] 徐吉庆[1] 孙浩然[1] 宋玉江[1] 

机构地区：[1]吉林大学化学系,长春130023

出　　处：《化学研究》2000年第2期9-13,共5页Chemical Research

基　　金：国家自然科学基金! ( 2 973 3 0 90 ;2 980 3 0 0 3 );高等学校博士学科点专项科研基金!资助项目

摘　　要：采用紫外可见吸收光谱研究了meso -四 ( 4 -N -甲基吡啶基 )卟啉 (M1 TMPyP ,M1 =H2 ,Zn)阳离子与金属-氧簇阴离子 (SiW1 2 O40 4 - )在水溶液中的光谱行为 .光谱演变及Job′s图表明M1 TMPyP与SiW1 2 O40 4 - 在水溶液中可形成相对稳定的 1∶1的超分子化合物。溶液的紫外可见吸收谱图明显不同于未相互作用的反应物吸收谱图的加和 ,表明有新化合物生成 ,且卟啉的发色团与SiW1 2 O40 4 - 通过静电发生强相互作用 ,同时考察了化学计量为1∶1的 [CoTMPyP][SiW1 2 O40 ]超分子化合物的电催化氧还原活性及其稳定性 ,表明该类超分子化合物有望成为新一类的催化氧还原的修饰电极材料。Spectral behavior of meso-tetrakis(4-N-methylpyridyl)porphyrin-metal-oxo cluster (SiW 12 O 40 4- )supramolecular systems in aqueous solution were studied by UV-visible spectrometry. The spectral evolution and Job's plots reveal that the relatively stable aggregates contain equal numbers of the cationic porphyrins and the anionic SiW 12 O 40 4- . The spectrum of the solution is different from the sum of those of individual reactants, revealing the formation of new species in which the porphyrin chromophores interact strongly with the metal-oxo clusters in the electrostatic interaction. The electrocatalytic behavior reducing O 2, for the 1∶1 supramolecular complex [CoTMPyP][SiW 12 O 40 ],is investigated, which is expected to be a new material of modified electrodes for electrocatalytic reduction of O 2.

关 键 词：阳离子卟啉 金属-氧簇阴离子 超分子化合物 

分 类 号：O641.4[理学—物理化学] O626.13[理学—化学]