Composition Tailoring via N and S Co‐doping and Structure Tuning by Constructing Hierarchical Pores: Metal‐Free Catalysts for High‐Performance Electrochemical Reduction of CO2

A facile route to scalable production of N and S co-doped, hierarchically porous carbon nanofiber (NSHCF) membranes (ca. 400 cm² membrane in a single process) is reported. As-synthesized NSHCF membranes are flexible and free-standing, allowing their direct use as cathodes for efficient electrochemical CO₂ reduction reaction (CO₂ RR). Notably, CO with 94 % Faradaic efficiency and -103 mA cm^-2 current density are readily achieved with only about 1.2 mg catalyst loading, which are among the best results ever obtained by metal-free CO₂ RR catalysts. On the basis of control experiments and DFT calculations, such outstanding CO Faradaic efficiency can be attributed to the co-doped pyridinic N and carbon-bonded S atoms, which effectively decrease the Gibbs free energy of key *COOH intermediate. Furthermore, hierarchically porous structures of NSHCF membranes impart a much higher density of accessible active sites for CO₂ RR, leading to the ultra-high current density.