Solid-state stepwise temperature-programmable synthesis of bioinspired Fe-N-C oxygen reduction electrocatalyst featuring Fe-N ₅ configuration

The bioinspired Fe-N-C features an asymmetric Fe-N₅ configuration to produce active metal-oxygen intermediates by introducing axial N ligand into a symmetric Fe-N₄ structure, enabling highly active oxygen reduction reaction (ORR). However, the artificial creation of active Fe-N₅ configuration with a direct, facile and green method has been rarely developed yet, as current techniques involve complex processes and costly precursors. Herein, we advance a novel solid-state stepwise temperature-programmable (SST) route to directly produce bioinspired Fe-N₅-C. We then demonstrate that such a Fe-N₅-C exhibits a quite higher half-wave potential (0.92 V) with 22-fold faster ORR kinetics (15.6 mA cm⁻² @ 0.85 V) over that of the commercial Pt/C counterpart. Indeed, we perform density functional theory (DFT) to find that the Fe is discharged with an extra 0.1 e⁻ through the axially coordinate N ligand, which significantly enhances the ability to activate O₂ and enables an easier desorption of the crucial intermediate *OH on the Fe-N₅ configuration over the conventional Fe-N₄ structure.