Modulation Engineering of Graphitic/Pyrrolic Nitrogen Co‐Doped Porous Carbon‐Based Electrocatalysts with Abundant Active Sites for Efficient CO ₂ Reduction

Developing metal‐free catalysts is critical to addressing the issues of susceptibility to poisoning and deficient durability in the electrocatalysis of metal‐based materials for CO 2 reduction reaction (CO 2 RR). Herein, N‐doped carbon nanoparticles (NCs) with a specific ratio of graphitic/pyrrolic N, high specific surface area, and abundant nanopores are synthesized by pyrolyzing a Cu and Zn co‐coordinated polymer with bis(imino)‐pyridine ligands. Results demonstrate that precise co‐incorporation of Cu and Zn in the precursor effectively modulates the N doping species and ratios of NCs, as well as the pore structure, resulting in significantly distinct CO 2 RR behaviors. The NCs synthesized by the precursor with the ratio of Zn and Cu ions (1 : 4), featuring graphitic‐N and pyrrolic‐N in the ratio of 2 : 1 and high specific surface area (896.8 m 2 g −1 ), exhibit a low onset potential of −0.4 V RHE , an exceptional CO Faradaic efficiency of 96.1 %, and a power density of 0.8 mW cm −2 in a Zn−CO 2 battery. Theory calculations reveal that regulating the graphitic/pyrrolic N ratio can redistribute the localized atoms′ charge density, which enhances the adsorption of intermediate COOH* and mobilizes multiple active atomic sites favoring CO 2 RR. The discovery in this work provides a new understanding for the design of advanced metal‐free CO 2 RR electrocatalysts.