Issue 4, 2015

Turning it off! Disfavouring hydrogen evolution to enhance selectivity for CO production during homogeneous CO2 reduction by cobalt–terpyridine complexes

Abstract

Understanding the activity and selectivity of molecular catalysts for CO2 reduction to fuels is an important scientific endeavour in addressing the growing global energy demand. Cobalt–terpyridine compounds have been shown to be catalysts for CO2 reduction to CO while simultaneously producing H2 from the requisite proton source. To investigate the parameters governing the competition for H+ reduction versus CO2 reduction, the cobalt bisterpyridine class of compounds is first evaluated as H+ reduction catalysts. We report that electronic tuning of the ancillary ligand sphere can result in a wide range of second-order rate constants for H+ reduction. When this class of compounds is next submitted to CO2 reduction conditions, a trend is found in which the less active catalysts for H+ reduction are the more selective towards CO2 reduction to CO. This represents the first report of the selectivity of a molecular system for CO2 reduction being controlled through turning off one of the competing reactions. The activities of the series of catalysts are evaluated through foot-of-the-wave analysis and a catalytic Tafel plot is provided.

Graphical abstract: Turning it off! Disfavouring hydrogen evolution to enhance selectivity for CO production during homogeneous CO2 reduction by cobalt–terpyridine complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
04 Dec 2014
Accepted
18 Feb 2015
First published
18 Feb 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 2522-2531

Turning it off! Disfavouring hydrogen evolution to enhance selectivity for CO production during homogeneous CO2 reduction by cobalt–terpyridine complexes

N. Elgrishi, M. B. Chambers and M. Fontecave, Chem. Sci., 2015, 6, 2522 DOI: 10.1039/C4SC03766A

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