Template‐Assisted Construction of Atomically Dispersed Fe‐N‐C Catalysts With Dense Fe‐N ₄ C Sites for Enhanced Oxygen Reduction Reaction

Atomically dispersed iron–nitrogen–carbon (Fe‐N‐C) catalysts have emerged as promising alternatives for oxygen reduction reaction (ORR) owing to their highly atomic utilization. However, maintaining both Fe atomic dispersion and dense Fe‐N x sites (typically below 2 wt%) in Fe‐N‐C catalysts is still a key challenge. In this investigation, a template (1,2‐dicyanobenzene; DCB) assisted strategy has been reported to achieve hierarchically porous Fe‐N/C DCB0.2 ‐900°C catalysts, which have atomically dispersed Fe‐N 4 C active sites with a 5.45 wt% Fe loading and served for robust ORR. 1,2‐dicyanobenzene containing abundant nitrogen source not only efficiently enhances the coordinated environment for dense Fe sites, but also facilitates the formation of a hierarchical porous structure in Fe‐N/C DCB0.2 ‐900°C catalyst. Computational analysis demonstrated that template‐assisted structural modification effectively reduces the energy barrier associated with *OOH intermediate formation while simultaneously adjusting the d‐band center position of Fe‐N 4 C coordination sites within the Fe‐N/C DCB0.2 ‐900°C system. This optimization enhances the stabilization of oxygen‐bearing intermediates and promotes accelerated kinetics of the ORR. Consequently, the Fe‐N/C DCB0.2 ‐900°C exhibited a half‐potential of 0.9 V versus RHE when evaluated in 0.1 M KOH electrolyte and achieved a peak power density of 220 mW cm −2 in a zinc–air battery, surpassing commercial Pt/C (0.88 V vs. RHE, 194 mW cm −2 ). Such methodology provides a new avenue for constructing dense metal active sites for achieving functional, but not limited to, ORR, catalysts and applications.