Boosting the Ni–Zn interplay via O/N dual coordination for high‐efficiency CO₂ electroreduction

Abstract Design of supportive atomic sites with a controllably adjusted coordinating environment is essential to advancing the reduction of CO₂ to value‐added fuels and chemicals and to achieving carbon neutralization. Herein, atomic Ni (Zn) sites that are uniquely coordinated with ternary Zn (Ni)/N/O ligands were successfully decorated on formamide‐derived porous carbon nanomaterials, possibly forming an atomic structure of Ni(N₂O₁)‐Zn(N₂O₁), as studied by combining X‐ray photoelectron spectroscopy and X‐ray absorption spectroscopy. With the mediation of additional O coordination, the Ni–Zn dual site induces significantly decreased desorption of molecular CO. The NiZn‐NC decorated with rich Ni(N₂O₁)‐Zn(N₂O₁) sites remarkably gained >97% CO Faraday efficiency over a wide potential range of ‒0.8 to ‒1.1 V (relative to reversible hydrogen electrode). Density functional theory computations suggest that the N/O dual coordination effectively modulates the electronic structure of the Ni–Zn duplex and optimizes the adsorption and conversion properties of CO₂ and subsequent intermediates. Different from the conventional pathway of using Ni as the active site in the Ni–Zn duplex, it is found that the Ni‐neighboring Zn sites in the Ni(N₂O₁)‐Zn(N₂O₁) coordination showed much lower energy barriers of the CO₂ protonation step and the subsequent dehydroxylation step.