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Abstract

Iron–nitrogen–carbon (Fe–N–C) materials have emerged as a promising alternative to platinum-group metals for catalyzing the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells. However, their low intrinsic activity and stability are major impediments. Herein, an Fe–N–C electrocatalyst with dense FeN₄ sites on hierarchically porous carbons with highly curved surfaces (denoted as FeN₄-hcC) is reported. The FeN₄-hcC catalyst displays exceptional ORR activity in acidic media, with a high half-wave potential of 0.85 V (versus reversible hydrogen electrode) in 0.5 m H₂SO₄. When integrated into a membrane electrode assembly, the corresponding cathode displays a high maximum peak power density of 0.592 W cm⁻² and demonstrates operating durability over 30 000 cycles under harsh H₂/air conditions, outperforming previously reported Fe–N–C electrocatalysts. These experimental and theoretical studies suggest that the curved carbon support fine-tunes the local coordination environment, lowers the energies of the Fe d-band centers, and inhibits the adsorption of oxygenated species, which can enhance the ORR activity and stability. This work provides new insight into the carbon nanostructure–activity correlation for ORR catalysis. It also offers a new approach to designing advanced single-metal-site catalysts for energy-conversion applications.