Meso/Microporous Single‐Atom Catalysts Featuring Curved Fe−N4 Sites Boost the Oxygen Reduction Reaction Activity

Zeolitic-imidazolate frameworks (ZIFs) are among the most efficient precursors for the synthesis of atomically dispersed Fe-N/C materials, which are promising catalysts for enhancing the performance of Zn-air batteries (ZABs) and proton exchange fuel cells (PEMFCs). However, existing ZIF-derived Fe-N/C electrocatalysts mostly consist of microporous materials, leading to insufficient mass transport and inadequate battery/cell performance. In this study, we synthesize an atomically dispersed meso/microporous Fe-N/C material with curved Fe-N₄ active sites, denoted as FeSA-N/TC, through the pyrolysis of hemin-modified ZIF films on ZnO nanorods, obtained from the self-assembly reaction between Zn²⁺ from ZnO hydrolysis and 2-methylimidazole. Density functional theory calculations demonstrate that the curved Fe-N₄ active sites can weaken the intermediate adsorptions, resulting in lower free energy barriers and enhanced performance during oxygen reduction reaction (ORR). Specifically, FeSA-N/TC exhibits exceptional ORR performance with half-wave potentials of 0.925 V in alkaline media and 0.825 V in acidic media. When used as the cathodic catalyst in PEMFCs and ZABs, FeSA-N/TC achieves high peak power densities (H₂-O₂ PEMFC: 1100 mW cm^-2; H₂-Air PEMFC: 715 mW cm^-2; liquid-state ZAB: 228 mW cm^-2; solid-state ZAB: 112 mW cm^-2), demonstrating its feasibility and efficiency in practical applications.