A new highly efficient tetra-electronic catalyst based on a cobalt porphyrin bound to four μ3-oxo-ruthenium acetate clusters

被引：57

作者：

Araki, K ^{[1
]}

Dovidauskas, S ^{[1
]}

Winnischofer, H ^{[1
]}

Alexiou, ADP ^{[1
]}

Toma, HE ^{[1
]}

机构：

[1] Univ Sao Paulo, Inst Quim, BR-05513970 Sao Paulo, SP, Brazil

来源：

JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 2001年 / 498卷 / 1-2期

基金：

巴西圣保罗研究基金会;

关键词：

supramolecular porphyrins; cobalt porphyrin; electrocatalysis; dioxygen reduction;

D O I：

10.1016/S0022-0728(00)00348-X

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

A meso-tetra(4-pyridyl)cobaltporphyrin modified with four [mu (3)-O-Ru-3(Ac)(6)(py)(2)](+) clusters (CoTCP = cobalt tetraclusterporphyrin) has been synthesized and characterized by H-1-NMR and UV-Vis spectroscopy, electrochemistry and spectroelectrochemistry. The facility of CoTCP to form adherent and durable films on a glassy carbon surface has been exploited in the preparation of modified electrodes exhibiting outstanding catalytic activity in the tetraelectronic reduction of dioxygen to water. This finding has been confirmed from the linear behavior and the slope of the Levich plots up to 4000 rpm, as well as from the high current densities, e.g. up to 2.8 mA cm(-2) obtained for the modified electrodes. The enhanced activity has been interpreted in terms of the electronic activation of the cobalt porphyrin by the peripheral triangular ruthenium cluster complexes, as supported by detailed spectroelectrochemical data confirming a significant electronic coupling between the cobalt porphyrin and [mu (3)-O-Ru-3(Ac)(6)](+) groups. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：152 / 160

页数：9