Co₄(SO₄)₄ Cluster‐Based Metal Porphyrin Frameworks Derived CoM‐NSC Materials for Efficient Oxygen Electrocatalysis

Zn–air batteries, recognized as safe, eco‐friendly, and efficient energy conversion/storage devices, function via oxygen reduction (ORR) and oxygen evolution (OER) reactions. However, the sluggish kinetics of these reactions significantly limit battery efficiency and currently necessitate expensive precious metal catalysts. Consequently, research focuses on developing cost‐effective transition metal, nitrogen‐doped carbon (M–N–C) materials as alternatives. Herein, we synthesized bimetallic CoM‐based sulfur‐doped nitrogen–carbon (CoM‐NSC) catalysts through pyrolysis of novel Co 4 (SO 4 ) 4 cluster‐based metal porphyrin frameworks (Co 4 ‐M‐MOFs; M═Co and Zn). The resulting CoCo‐NSC integrated with carbon nanotubes (CNTs) exhibits exceptional bifunctional catalytic activity, achieving an ORR half‐wave potential ( E 1/2 ) of 0.88 V (versus reversible hydrogen electrode, versus RHE) in 0.1 M KOH and an OER overpotential ( η 10 ) of 286 mV in 1.0 M KOH at a current density of 10 mA cm −2 . Furthermore, it demonstrates remarkable methanol tolerance and long‐term stability. CoCo‐NSC also exhibited good Zn–air battery performance with a peak power density of 250 mW cm −2 , outperforming the benchmark Pt/C + RuO 2 (137 mW cm −2 ). This work presents an efficient synthetic strategy for designing sulfur‐doped M–N–C electrocatalysts with enhanced electrocatalytic activity and stability.