Simultaneously Boosting Graphitization and Nitrogen Doping of Carbon Catalysts for Enhanced Alkaline Oxygen Reduction Reaction Catalytic Activity

Oxygen reduction reaction (ORR) is pivotal in energy conversion devices. Metal‐free nitrogen‐doped carbon (NC) catalysts are promising for alkaline ORR. Yet, the tradeoff between graphitization and nitrogen doping limits their catalytic activity. Herein, a strategy to enhance graphitization and nitrogen doping simultaneously by coupling hydrogen (H 2 ) gas and urea into the pyrolysis of a metal–organic framework (i.e., ZIF‐8) precursor is reported. Introducing 7.5 vol% H 2 promotes selective carbon gasification, improving graphitic structures, while urea compensates for nitrogen loss and enriches graphitic‐N. The optimized NC catalyst achieves a high half‐wave potential (0.85 V RHE ), a current density of 5.56 mA cm − 2 at 0.3 V RHE , and a low Tafel slope of 57 mV dec − 1 in 0.1 M KOH electrolyte, comparable to commercial 20 wt% Pt/C catalysts. Improved graphitization (G/D ratio of 0.973) and an increased relative abundance of graphitic‐N (20.0 at%) correlate with enhanced intrinsic catalytic activity. Furthermore, a primary zinc‐air battery using the optimized NC catalyst exhibits superior performance, delivering a maximum power density of 140 mW cm − 2 and a specific discharge capacity of 722 mAh g Zn −1 . This work presents a novel approach to designing high‐performance metal‐free carbon catalysts by tailoring pyrolysis environments to strike a balance between graphitization and nitrogen doping.