The development of efficient single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) remains a formidable challenge, primarily due to the symmetric charge distribution of metal single-atom sites (M-N₄). To address such issue, herein, Fe-N_x sites coupled synergistic catalysts fabrication strategy is presented to break the uniform electronic distribution, thus enhancing the intrinsic catalytic activity. Precisely, atomically dispersed Fe-N_x sites supported on N/S-doped mesoporous carbon (NSC) coupled with FeS@C core-shell nanoparticles (FAS-NSC@950) is synthesized by a facile hydrothermal reaction and subsequent pyrolysis. Due to the presence of an in situ-grown conductive graphitic layer (shell), the FeS nanoparticles (core) effectively adjust the electronic structure of single-atom Fe sites and facilitate the ORR kinetics via short/long-range coupling interactions. Consequently, FAS-NSC@950 displays a more positive half-wave potential (E_1/2) of 0.871 V with a significantly boosted ORR kinetics (Tafel slope = 52.2 mV dec⁻¹), outpacing the commercial Pt/C (E_1/2 = 0.84 V and Tafel slope = 54.6 mV dec⁻¹). As a bifunctional electrocatalyst, it displays a smaller bifunctional activity parameter (ΔE) of 0.673 V, surpassing the Pt/C-RuO₂ combination (ΔE = 0.724 V). Besides, the FAS-NSC@950-based zinc-air battery (ZAB) displays superior power density, specific capacity, and long-term cycling performance to the Pt/C-Ir/C-based ZAB. This work significantly contributes to the field by offering a promising strategy to enhance the catalytic activity of SACs for ORR, with potential implications for energy conversion and storage technologies.

开发用于氧还原反应（ORR）的高效单原子催化剂（SAC）仍然是一个艰巨的挑战，这主要是由于金属单原子位点（MN ₄）的对称电荷分布。为了解决这个问题，本文提出了Fe-N _{x位点耦合协同催化剂的制备策略，以打破均匀的电子分布，从而增强固有的催化活性。}准确地说，通过简单的水热反应和随后的热解合成了负载在N/S掺杂介孔碳（NSC）上的原子分散的Fe-N _x位点以及FeS@C核壳纳米粒子（FAS-NSC@950）。由于存在原位生长的导电石墨层（壳），FeS纳米颗粒（核）有效地调节单原子Fe位点的电子结构，并通过短程/长程耦合相互作用促进ORR动力学。因此，FAS-NSC@950 显示出 0.871 V 的更正半波电位 ( E _1/2 )，并显着增强 ORR 动力学（塔菲尔斜率 = 52.2 mV dec ^-1），超过了商用 Pt/C ( E _{1 /2}  = 0.84 V 且塔菲尔斜率 = 54.6 mV dec ^-1 )。作为一种双功能电催化剂，它表现出较小的双功能活性参数（Δ E）为0.673 V，超过了Pt/C-RuO ₂组合（Δ E  = 0.724 V）。此外，FAS-NSC@950基锌空气电池（ZAB）比Pt/C-Ir/C基ZAB表现出优越的功率密度、比容量和长期循环性能。这项工作通过提供一种有前途的策略来增强 SAC 对 ORR 的催化活性，对该领域做出了重大贡献，并对能量转换和存储技术具有潜在影响。