In-Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO Reduction to Ethylene.

Bridging homogeneous molecular systems with heterogeneous catalysts is a promising approach for the development of new electrodes, combining the advantages of both approaches. In the context of CO electroreduction, molecular enhancement of planar copper electrodes has enabled promising advancement towards high Faradaic efficiencies for multicarbon products. Besides, nanostructured copper electrodes have also demonstrated enhanced performance at comparatively low overpotentials. Herein, we report a novel and convenient method for nanostructuring copper electrodes using N,N'-ethylene-phenanthrolinium dibromide as molecular additive. Selectivities up to 70 % for C products are observed for more than 40 h without significant change in the surface morphology. Mechanistic studies reveal several roles for the organic additive, including: the formation of cube-like nanostructures by corrosion of the copper surface, the stabilization of these nanostructures during electrocatalysis by formation of a protective organic layer, and the promotion of C products.