Adjusting the Adsorption of Key Intermediates in Alloyed Ni 3 ZnC 0.7 /G Enhanced Performance Towards CO 2 Electroreduction to CO

Electrochemical carbon dioxide reduction reaction (eCO 2 RR) is an effective method for promoting the construction of a carbon circular economy. The alloyed Ni 3 ZnC 0.7 /G catalyst was prepared by pyrolyzing the bimetallic zeolitic imidazolate frameworks (ZIFs) embodied in the graphene oxide. The prepared catalyst exhibited excellent CO Faradaic efficiency (FE CO ) and reached a maximum of 99.43% (−0.95 V vs RHE), surpassing the performance of the catalyst Ni/G. During 60 hours of electrolysis, Ni 3 ZnC 0.7 /G maintained a stable current density above 30 mA cm −2 and a FE CO of over 80%. The characterization results revealed that the pure phase of Ni 3 ZnC 0.7 was formed, assisted by the porous carbon substrate, and the as-formed catalyst demonstrated a higher electrochemically active surface area in the eCO 2 RR. X-ray photoelectron spectroscopy (XPS), in situ ATR-SEIRAS, and Density functional theory (DFT) calculations suggested a facile electron transfer from Zn to Ni, and the nitrogen-doped carbon substrate significantly enhanced the electron transfer rate. The increased electronic density of Ni site in Ni 3 ZnC 0.7 /G improved the *COOH species formation, simultaneously weakening the adsorption of *CO, thereby promoting the generation of CO and suppressing the hydrogen evolution reaction.