Interfacial Oxidation Nanoarchitectonics of Water‐Soluble C ₆₀ Towards High‐Performance Fe–N–C Electrocatalysts

The chemical modification and self‐assembly capability of fullerenes offer advantageous conditions for tailoring Fe/N‐doped carbon‐based catalysts. However, their strong π–π stacking tendency may partially restrict metal loading and the generation of active Fe species. Therefore, how to utilize the distinctive features of fullerenes to precisely regulate and optimize Fe–N active sites along with their local coordination environment remains challenging. In this work, water‐soluble C 60 (wsC 60 ) was synthesized via a facile interfacial oxidation process. The presence of –OH on the C 60 cage may strengthen its binding affinity with Fe 3+ ion and effectively modulate the incorporation of Fe/N into the C 60 ‐derived carbon electrodes. By varying the wsC 60 /Fe 3+ mixing ratios followed by pyrolysis under NH 3 , we obtained Fe/N‐doped carbons (FeN@wsC 60 ‐900) with distinct Fe/N‐doping states, including FeN 4 , O–FeN 4 /Fe cluster, and FeN 4 /Fe cluster. The abundant –OH in wsC 60 also promoted the formation of a highly porous network, enhancing active site accessibility. The resultant FeN@wsC 60 ‐900 exhibited excellent oxygen reduction reaction (ORR) activity, outperforming both conventional C 60 ‐derived carbons and commercial Pt/C. Structural characterizations and density functional theory (DFT) simulations revealed that the O‐coordinated Fe–N 4 with adjacent Fe cluster could optimize the coordinate geometry and adsorption energies of key ORR intermediates.