FeN₄OC Nanoplates Covalently Bonding on Graphene for Efficient CO₂ Electroreduction and ZnCO₂ Batteries

Abstract Electrochemical carbon dioxide (CO₂) reduction into value‐added products holds great promise in moving toward carbon neutrality but remains a grand challenge due to lack of efficient electrocatalysts. Herein, the nucleophilic substitution reaction is elaborately harnessed to synthesize carbon nanoplates with a FeN₄O configuration anchored onto graphene substrate (FeN₄OC/Gr) through covalent linkages. Density functional theory calculations demonstrate the unique configuration of FeN₄O with one oxygen (O) atom in the axial direction not only suppresses the competing hydrogen evolution reaction, but also facilitates the desorption of *CO intermediate compared with the commonly planar single‐atomic Fe sites. The FeN₄OC/Gr shows excellent performance in the electroreduction of CO₂ into carbon monoxide (CO) with an impressive Faradaic efficiency of 98.3% at −0.7 V versus reversible hydrogen electrode (RHE) and a high turnover frequency of 3511 h⁻¹. Furthermore, as a cathode catalyst in an aqueous zinc (Zn)‐CO₂ battery, the FeN₄OC/Gr achieves a high CO Faradaic efficiency (≈91%) at a discharge current density of 3 mA cm⁻² and long‐term stability over 74 h. This work opens up a new route to simultaneously modulate the geometric and electronic structure of single‐atomic catalysts toward efficient CO₂ conversion.