Synergistic Dual‐Atom Molecular Catalyst Derived from Low‐Temperature Pyrolyzed Heterobimetallic Macrocycle‐N4 Corrole Complex for Oxygen Reduction

Abstract A heterobimetallic corrole complex, comprising oxygen reduction reaction (ORR) active non‐precious metals Co and Fe with a corrole‐N4 center (PhFCC), is successfully synthesized and used to prepare a dual‐atom molecular catalyst (DAMC) through subsequent low‐temperature pyrolysis. This low‐temperature pyrolyzed electrocatalyst exhibited impressive ORR performance, with onset potentials of 0.86 and 0.94 V, and half‐wave potentials of 0.75 and 0.85 V, under acidic and basic conditions, respectively. During potential cycling, this DAMC displayed half‐wave potential losses of only 25 and 5 mV under acidic and alkaline conditions after 3000 cycles, respectively, demonstrating its excellent stability. Single‐cell Nafion‐based proton exchange membrane fuel cell performance using this DAMC as the cathode catalyst showed a maximum power density of 225 mW cm⁻², almost close to that of most metal–N4 macrocycle‐based catalysts. The present study showed that preservation of the defined CoN4 structure along with the cocatalytic Fe–Cx site synergistically acted as a dual ORR active center to boost overall ORR performance. The development of DAMC from a heterobimetallic CoN4‐macrocyclic system using low‐temperature pyrolysis is also advantageous for practical applications.