Fullerene Fragment Restructuring: How Spatial Proximity Shapes Defect-Rich Carbon Electrocatalysts

Fullerene transformation emerges as a powerful route to construct defect-rich carbon electrocatalysts, but the carbon bond breakage and reformation that determine the defect states remain poorly understood. Here, we explicitly reveal that the spatial proximity of disintegrated fullerene imposes a crucial impact on the bond reformation and electrocatalytic properties. A counterintuitive hard-template strategy is adopted to enable the space-tuned fullerene restructuring by calcining impregnated C₆₀ not only before but also after the removal of rigid silica spheres (∼300 nm). When confined in the SiO₂ nanovoids, the adjacent C₆₀ fragments form sp³ bonding with adverse electron transfer and active site exposure. In contrast, the unrestricted fragments without SiO₂ confinement reconnect at the edges to form sp²-hybridized nanosheets while retaining high-density intrinsic defects. The optimized catalyst exhibits robust alkaline oxygen reduction performance with a half-wave potential of 0.82 V via the 4e^- pathway. Copper poisoning affirms the intrinsic defects as the authentic active sites. Density functional theory calculations further substantiate that pentagons in the basal plane lead to localized structural distortion and thus exhibit significantly reduced energy barriers for the first O₂ dissociation step. Such space-regulated fullerene restructuring is also verified by heating C₆₀ crystals confined in gallium liquid and a quartz tube.