Attenuating metal-substrate conjugation in atomically dispersed nickel catalysts for electroreduction of CO(2) to CO

Atomically dispersed transition metals on carbon-based aromatic substrates are an emerging class of electrocatalysts for the electroreduction of CO(2). However, electron delocalization of the metal site with the carbon support via d-π conjugation strongly hinders CO(2) activation at the active metal centers. Herein, we introduce a strategy to attenuate the d-π conjugation at single Ni atomic sites by functionalizing the support with cyano moieties. In situ attenuated total reflection infrared spectroscopy and theoretical calculations demonstrate that this strategy increases the electron density around the metal centers and facilitates CO(2) activation. As a result, for the electroreduction of CO(2) to CO in aqueous KHCO(3) electrolyte, the cyano-modified catalyst exhibits a turnover frequency of ~22,000 per hour at −1.178 V versus the reversible hydrogen electrode (RHE) and maintains a Faradaic efficiency (FE) above 90% even with a CO(2) concentration of only 30% in an H-type cell. In a flow cell under pure CO(2) at −0.93 V versus RHE the cyano-modified catalyst enables a current density of −300 mA/cm(2) with a FE above 90%.