Transition metal compound (TMC)/carbon hybrids, as prospering electrocatalyst, have attracted great attention in the field of oxygen reduction reaction (ORR). Their morphology, structure and composition often play a crucial role in determining the ORR performance. In this work, we for the first time report the successful fabrication of porous core–shell Fe_1−xS@N, S co-doped carbon (Fe_1−xS@NSC-t, t represents etching time) by a novel in-situ self-template induced strategy using Fe₃O₄ nanospheres and pyrrole as sacrificial self-template. The post-polymerization of pyrrole can be accomplished by the Fe³⁺ released through the etching of Fe₃O₄ by HCl acid. Thus, the etching time has a significant effect on the morphology, structure, composition and ORR performance of Fe_1−xS@NSC-t. Based on the characterizations, we find Fe_1−xS@NSC-24 can realize effective and balanced combination of Fe_1−xS and NSC, possessing porous core–shell architecture, optimized structure defect, specific surface area and doped heteroatoms configurations (especially for pyridinic N, graphitic N and Fe-N structure). These features thus lead to outstanding catalytic activity and cycling stability towards ORR. Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.

过渡金属化合物（TMC）/碳杂化物作为繁荣的电催化剂，在氧还原反应（ORR）领域引起了极大的关注。它们的形态，结构和组成通常在决定ORR性能方面起着至关重要的作用。在这项工作中，我们首次报道了通过新颖的方法成功地制造了多孔核-壳Fe ₁ - _x S @ N，S共掺杂碳（Fe _{1- x} S @ NSC- t，t表示蚀刻时间）在-原位自模板，使用铁诱导的策略₃ ö ₄纳米球和吡咯作为牺牲自模板。吡咯的后聚合可通过Fe来完成通过盐酸腐蚀Fe ₃ O ₄释放出³⁺。因此，刻蚀时间对Fe _{1- x} S @ NSC- t的形貌，结构，组成和ORR性能具有重要影响。根据表征，我们发现Fe ₁ - _x S @ NSC-24可以实现Fe _{1- x的}有效平衡平衡S和NSC具有多孔核-壳结构，优化的结构缺陷，比表面积和掺杂的杂原子构型（特别是对于吡啶N，石墨N和Fe-N结构而言）。这些特征因此导致优异的催化活性和对ORR的循环稳定性。我们的工作为TMC /碳基电极的设计提供了良好的指导，这些电极具有独特的稳定形态和优化的结构与成分。