Electrode-Ligand Interactions Dramatically Enhance CO2 Conversion to CO by the [Ni(cyclam)](PF6)2 Catalyst

Dramatic enhancement of electrochemical CO2 conversion to CO, catalyzed by [Ni(cyclam)](PF6)(2) is observed on mercury/gold electrodes. We find that Hg provides favorable noncovalent dispersive interactions with the cyclam ligand. As a result, the Hg surface destabilizes the poisoned CO-bound form of the catalyst, leading to enhanced reaction kinetics. These findings are particularly relevant to the design of ligands that improve the electrocatalytic performance of transition-metal complexes on interaction with metallic surfaces under cell operating conditions.