Proton-coupled electron transfer kinetics for the hydrogen evolution reaction of hangman porphyrins

被引：148

作者：

Roubelakis, Manolis M. ^{[1
]}

Bediako, D. Kwabena ^{[1
]}

Dogutan, Dilek K. ^{[1
]}

Nocera, Daniel G. ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

ENERGY & ENVIRONMENTAL SCIENCE | 2012年 / 5卷 / 07期

关键词：

SOLAR-ENERGY; MOLECULAR CATALYSTS; CONCERTED PROTON; H-2; PRODUCTION; COMPLEXES; RELAYS; WATER; ACTIVATION; OXIDATION; CHEMISTRY;

D O I：

10.1039/c2ee21123h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cobalt hangman porphyrins catalyze the hydrogen evolution reaction (HER). The hangman group is observed to facilitate HER by mediating a proton-coupled electron transfer (PCET) reaction. The details of the PCET pathway have been determined by comparing rate constants associated with the ET and PT processes of the hangman system to those of the corresponding values measured for porphyrins that lack an internal proton relay. A rapid intramolecular proton transfer from the carboxylic acid hanging group to the reduced cobalt centre of 8.5 x 10(6) s(-1) provides a facile pathway for the formation of Co(II) H, which leads directly to H-2 generation.

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收藏

页码：7737 / 7740

页数：4

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