Facile Synthesis of Thiophene‐Based MOF‐Derived Bimetallic ZnM Sulfides (M═Fe, Co, Ni) for Electrocatalytic Oxygen Reduction and Zinc Air Batteries

ABSTRACT Transition metal sulfides (TMSs) have emerged as promising catalysts for the oxygen reduction reaction (ORR), yet achieving activity comparable to Pt‐based benchmarks remains challenging. Herein, we present an in situ MOF‐carbonization strategy to prepare transition metal‐doped ZnS nanoparticles embedded in N, S‐codoped carbon nanorods (M─ZnS/NSCNR, M═Fe, Co, Ni). Structural characterization confirms successful dopant integration into ZnS lattices within hierarchical carbon substrates, yielding enhanced defect density and optimal porosity. Furthermore, electrochemical evaluation reveals Fe─ZnS/NSCNR's exceptional ORR performance in 0.1 M KOH, exhibiting a half‐wave potential of 0.897 V and limiting current density of 5.20 mA cm ^−2— surpassing both Pt/C and Co/Ni analogues. In zinc‐air batteries, it can achieve a peak power density of 132.1 mW cm ⁻² , specific capacity of 685.6 mAh g _Zn ⁻¹ , and minimal voltage gap (0.96 V) during 70 h cycling. DFT calculations show that transition metal doping effectively modulates the ZnS electronic structure by adjusting the position of the d‐band center (d _ε ). The Fe‐doped ZnS model exhibits a well‐balanced d _ε value (−1.34 eV) and reduced OOH ^* adsorption barrier (0.62 eV), leading to enhanced ORR activity. This work establishes a scalable route for designing noble metal‐free, MOF‐derived ORR catalysts with superior activity‐durability characteristics for advanced energy technologies.