Turning it off! Disfavouring hydrogen evolution to enhance selectivity for CO production during homogeneous CO2 reduction by cobalt–terpyridine complexes† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03766a Click here for additional data file.

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.