Synergistic Cooperation of Active Sites in Cu-Incorporated Nitrogen-Doped Porous Carbon for CO2 Electroreduction to Ethanol.

Selective electroreduction of CO2 to ethanol has attracted increasing interest. Herein, we report an effective strategy to boost ethanol selectivity from electrocatalytic CO2 reduction by constructing Cu-incorporated nitrogen-doped porous carbon (Cu-NPC) via pyrolysis of bimetallic CuZn-MOF-74, followed by an etching treatment. Etching processes not only remove large-sized metal particles and create lots of pores in the catalyst but also leave Cu existing mainly as Cu+ that shows strong electronic interaction with the pyridinic N in NPC. Since pyridinic N is active for *CO formation and Cu+ is conducive to C-C coupling, the close proximity between these two sites results in synergistic cooperation to promote C-C coupling and efficiently reduce CO2 to ethanol with a high Faradaic efficiency (FE) of 77.1% at a low potential of -0.25 V (RHE), outperforming most of the previous reports. The highly porous structure and the synergistic cooperation of the active sites are proved conducive to the formation of *CO and *CHO, and their C-C coupling to form ethanol. This work provides an effective way for electrocatalyst design toward valuable C2+ product formation from CO2 reduction, featuring great significance for CO2 utilization and carbon neutralization.