Nitrogen-doped carbon supported metal single-atom catalysts (M-N-C SACs), especially Fe-N-C SACs appear as very promising catalysts for oxygen reduction reaction (ORR). However, precisely modulating of the Fe-N_x configuration and geometric microenvironment in Fe-N-C SACs to achieve the highest level of catalytic activity remains grand challenges. Herein, we describe a N-rich heterocycle regulated supramolecular coordination self-assembly strategy to fabricate Fe single atoms anchored on N-enriched porous submicron carbon spheres (FeSA/N-PSCS), with ultra-high N-dopant content (14.81 at.%) for facilitating the formation of atomically dispersed Fe-N₄. Density functional theory calculations validate that N-doping at the periphery of the Fe-N₄ active sites optimizes the adsorption of oxygen-containing intermediates and significantly reduces the ORR overpotential. Benefitting from the localized N-enriched atomic configuration, highly microporous, and regular submicron-spherical structure, FeSA/N-PSCS exhibit enhanced ORR performance. More importantly, FeSA/N-PSCS catalyzed Zn-air battery (ZAB) outperforms Pt/C+RuO₂-based ZAB in the aspects of maximum power density, specific capacity and cycling stability.

氮掺杂碳负载金属单原子催化剂 (MNC SAC)，尤其是 Fe-NC SAC 似乎是非常有前途的氧还原反应 (ORR) 催化剂。然而，精确调节 Fe-NC SAC 中的 Fe-Nx_构型和几何微环境以实现最高水平的催化活性仍然是巨大的挑战。在此，我们描述了一种富 N杂环调节的超分子配位自组装策略，以制造锚定在富 N 多孔亚微米碳球 (FeSA/N-PSCS) 上的 Fe 单原子，具有超高 N 掺杂含量（14.81 at. %) 以促进原子分散的 Fe-N ₄的形成。_{密度泛函理论计算验证了Fe-N 4}外围的N掺杂活性位点优化了含氧中间体的吸附，显着降低了 ORR 过电势。得益于局部富氮原子构型、高度微孔和规则的亚微米球形结构，FeSA/N-PSCS 表现出增强的 ORR 性能。更重要的是，FeSA/N-PSCS催化的锌空气电池（ZAB）在最大功率密度、比容量和循环稳定性方面优于Pt/C+RuO _2基ZAB。