Alloying Co Species into Ordered and Interconnected Macroporous Carbon Polyhedra for Efficient Oxygen Reduction Reaction in Rechargeable Zinc–Air Batteries

Engineering non-precious transition metal (TM)-based electrocatalysts to simultaneously achieve an optimal intrinsic activity, high density of active sites, and rapid mass transfer ability for the oxygen reduction reaction (ORR) remains a significant challenge. To address this challenge, a hybrid composite consisting of Fex Co alloy nanoparticles uniformly implanted into hierarchically ordered macro-/meso-/microporous N-doped carbon polyhedra (HOMNCP) is rationally designed. The combined results of experimental and theoretical investigations indicate that the alloying of Co enables a favorable electronic structure for the formation of the *OH intermediate, while the periodically trimodal-porous structured carbon matrix structure not only provides highly accessible channels for active site utilization but also dramatically facilitates mass transfer in the catalytic process. As expected, the Fe0.5 Co@HOMNCP composite catalyst exhibits extraordinary ORR activity with a half-wave potential of 0.903 V (vs reversible hydrogen electrode), surpassing most Co-based catalysts reported to date. More remarkably, the use of the Fe0.5 Co@HOMNCP catalyst as the air electrode in a zinc-air battery results in superior open-circuit voltage and power density compared to a commercial Pt/C + IrO2 catalyst. The results of this study are expected to inspire the development of advanced TM-based catalysts for energy storage and conversion applications.