Heterogeneous electrocatalytic reduction of CO2 promoted by secondary coordination sphere effects

The electrochemical conversion of CO2 to fuels and chemicals is a rapidly growing area of both scientific interest and technological importance. To overcome the challenges of low rates and selectivity on heterogeneous catalysts, efforts are being directed to harness enzyme-mimetic secondary coordination sphere effects to attain a further level of control. These include hydrogen bonding, electrostatics, complexation, and sterics to promote CO2 reduction down a desired pathway on the electrocatalyst surface. This focus review is centered on key advances made in recent years in utilizing secondary coordination sphere effects on heterogeneous catalysts. We discuss how the incorporation of rationally designed electrolyte additives, grafted surface ligands, and chemically tuneable porous scaffolds facilitates enhanced reactivity for CO2 reduction and what advances still need to be made in order to elevate this technology from the lab scale to economic feasibility.