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 C-60 not only before but also after the removal of rigid silica spheres (similar to 300 nm). When confined in the SiO2 nanovoids, the adjacent C-60 fragments form sp(3) bonding with adverse electron transfer and active site exposure. In contrast, the unrestricted fragments without SiO2 confinement reconnect at the edges to form sp(2)-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 O-2 dissociation step. Such space-regulated fullerene restructuring is also verified by heating C-60 crystals confined in gallium liquid and a quartz tube.

Automated summary

This study reveals the crucial impact of spatial proximity on fullerene restructuring and electrocatalytic properties, providing important guidance for constructing defect-rich carbon electrocatalysts. By adopting a hard-template strategy and confining the fullerene restructuring in SiO2 nanovoids, the formation of carbon bonds and the enhancement of electrocatalytic performance can be controlled. The optimized catalyst exhibits excellent performance in alkaline oxygen reduction reaction and authenticates intrinsic defects as the active sites.