Sol–gel pore‐confined strategy to synthesize atomically dispersed metal sites for enhanced <scp>CO₂</scp> electroreduction

Abstract Excavating highly efficient and cost‐effective non‐noble metal single‐atom catalysts for electrocatalytic CO 2 reduction reaction (CO 2 RR) is of paramount significance. However, the general and universal strategy for designing atomically dispersed metals as accessible active sites is still in its infancy. Herein, we reported a general sol–gel pore‐confined strategy for preparing a series of isolated transition metal single atoms (Fe/Co/Ni/Cu) anchored on nitrogen‐doped carbon matrix. Benefiting from synergistic effect of M‐N 4 coordination and neighboring N doping, the Fe‐N 4 ‐C catalyst exhibited superior capability with a Faradaic efficiency of 96.9%, achieving highly stable electrocatalytic activity for more than 20 h. Density functional theory (DFT) calculations further revealed the changes in the d xz orbital of Fe, with a decrease in the out‐of‐plane component. Thus, a lower free energy barrier (ΔG) in thermodynamic pathway and the accelerated proton transfer to *COOH in kinetic pathway both enhanced electrocatalytic process.