ELECTROCHEMICAL POLYMERIZATION OF AMINO-SUBSTITUTED, PYRROLE-SUBSTITUTED, AND HYDROXY-SUBSTITUTED TETRAPHENYLPORPHYRINS
ELECTROCHEMICAL POLYMERIZATION OF AMINO-SUBSTITUTED, PYRROLE-SUBSTITUTED, AND HYDROXY-SUBSTITUTED TETRAPHENYLPORPHYRINS
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DOI：
10.1021/ic00254a011
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发表时间：
1987-04-08
影响因子：
4.6
通讯作者：
MURRAY, RW
中科院分区：
文献类型：
--
作者：
BETTELHEIM, A;WHITE, BA;MURRAY, RW
本文报道了四（邻、间、对氨基苯基）卟啉、四（对二甲氨基苯基）卟啉、四（对羟基苯基）卟啉和四醛（对N-吡咯基苯基）卟啉及其镍、钴金属配合物的电化学聚合。这些单体的氧化导致薄的聚合物涂层电极上的耦合反应类似于那些在聚苯胺，聚吡咯，和多酚电聚合。该膜含有两层到几百层的卟啉位点，并显示出类似于单体在乙腈或二氯甲烷中的还原电化学和电子光谱性质。基于吡咯基和氨基的聚合物是聚阳离子，因此是阴离子交换剂，而基于羟基的聚合物（在pH> 8下）是聚阴离子。由钴四（邻氨基苯基）卟啉的电聚合制备的膜在酸和碱的水溶液中显示分裂Co（III/II）波，并且是良好的氧还原催化剂，而由所有其他钴卟啉单体制备的膜仅显示一个Co（III/II）波，并且是差的催化剂。
The electrochemical polymerizations of tetrakis (o-, m-, and p-aminophenyl) porphyrin, tetrakis (p-(dimethylamino) phenyl) porphyrin, tetrakis (p-hydroxyphenyl) porphyrin, and tetralds (pN-pyrrolylphenyl) porphyrin and their nickel and cobalt metalated complexes are described. Oxidations of these monomers lead to thin polymeric coatings on electrodes by coupling reactions analogous to those operative in polyaniline, polypyrrole, and polyphenol electropolymerization. Thefilms contain from two to several hundred layers of porphyrin sites and display reductive electrochemical and electronic spectroscopic properties similar to those of monomer solutions in acetonitrile or methylene chloride. The pyrrolyl-and amino-based polymers are polycationic and thus anion exchangers, whereas the hydroxy-based polymers (at pH> 8) are polyanionic. Films prepared from electropolymerization of cobalt tetra-kis (o-aminophenyl) porphyrin display a split Co (III/II) wave in aqueous acid and base and are good oxygen reduction catalysts, whereas films prepared from all other cobalt porphyrin monomers display only one Co (III/II) wave and are poor catalysts.