Electrochemistry, spectroelectrochemistry and catalytic activity of biscobalt bisporphyrin dyads towards dioxygen reduction

被引：18

作者：

Chen, Ping ^{[1
]}

Lau, Hoyi ^{[1
]}

Habermeyer, Benoit ^{[2
]}

Gros, Claude P. ^{[2
]}

Barbe, Jean-Michel ^{[2
]}

Kadish, Karl M. ^{[1
]}

机构：

[1] Univ Houston, Dept Chem, Houston, TX 77204 USA

[2] Univ Bourgogne, ICMUB, UMR 5260, F-21078 Dijon, France

来源：

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES | 2011年 / 15卷 / 5-6期

关键词：

cobalt porphyrins; tris-metal dyad; synthesis; electrochemistry; dioxygen reduction catalysis; PORPHYRIN-CORROLE DYADS; COFACIAL DICOBALT PORPHYRINS; ARYL SUBSTITUTED CORROLES; SINGLET ENERGY TRANSFERS; COBALT PORPHYRINS; ELECTRON-TRANSFER; 4-ELECTRON REDUCTION; GRAPHITE-ELECTRODES; PERCHLORIC-ACID; CARBON-MONOXIDE;

D O I：

10.1142/S1088424611003410

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Three face-to-face biscobalt bisporphyrin dyads, including one incorporating a copper(II) ion inside the linker, were synthesized and characterized both spectroscopically and electrochemically in three non-aqueous solvents, dichloromethane, benzonitrile and pyridine. The electrocatalytic reduction of dioxygen with these derivatives on an electrode surface in 1.0 M HClO(4) was also investigated and the results are compared to that obtained with "regular" Pacman biscobalt bisporphyrins under the same experimental conditions. Surprisingly, the tris-metal species (Cu-bisCo) catalyzes the reduction of O(2) mainly via a 2e(-) transfer process, leading to H(2)O(2), while the bis-metal (bisCo) catalyst produces H(2)O via a four electron, four proton process.

引用

收藏

页码：467 / 479

页数：13

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