Concurrently Boosting Activity and Stability of Oxygen Reduction Reaction Catalysts via Judiciously Crafting Fe–Mn Dual Atoms for Fuel Cells

The ability to unlock the interplay between the activity and stability of oxygen reduction reaction (ORR) represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells. Herein, we report an effective strategy to concurrent enhance the activity and stability of ORR catalysts via constructing atomically dispersed Fe-Mn dual-metal sites on N-doped carbon (denoted (FeMn-DA)-N-C) for both anion-exchange membrane fuel cells (AEMFC) and proton exchange membrane fuel cells (PEMFC). The (FeMn-DA)-N-C catalysts possess ample dual-metal atoms consisting of adjacent Fe-N₄ and Mn-N₄ sites on the carbon surface, yielded via a facile doping-adsorption-pyrolysis route. The introduction of Mn carries several advantageous attributes: increasing the number of active sites, effectively anchoring Fe due to effective electron transfer to Mn (revealed by X-ray absorption spectroscopy and density-functional theory (DFT), thus preventing the aggregation of Fe), and effectively circumventing the occurrence of Fenton reaction, thus reducing the consumption of Fe. The (FeMn-DA)-N-C catalysts showcase half-wave potentials of 0.92 and 0.82 V in 0.1 M KOH and 0.1 M HClO₄, respectively, as well as outstanding stability. As manifested by DFT calculations, the introduction of Mn affects the electronic structure of Fe, down-shifts the d-band Fe active center, accelerates the desorption of OH groups, and creates higher limiting potentials. The AEMFC and PEMFC with (FeMn-DA)-N-C as the cathode catalyst display high power densities of 1060 and 746 mW cm^-2, respectively, underscoring their promising potential for practical applications. Our study highlights the robustness of designing Fe-containing dual-atom ORR catalysts to promote both activity and stability for energy conversion and storage materials and devices.