Issue 7, 2012

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

Abstract

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 × 106 s−1 provides a facile pathway for the formation of Co(II)H, which leads directly to H2 generation.

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

Supplementary files

Article information

Article type
Communication
Submitted
16 jan 2012
Accepted
14 feb 2012
First published
14 feb 2012

Energy Environ. Sci., 2012,5, 7737-7740

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

M. M. Roubelakis, D. K. Bediako, D. K. Dogutan and D. G. Nocera, Energy Environ. Sci., 2012, 5, 7737 DOI: 10.1039/C2EE21123H

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