Curvature-induced electronic asymmetry in hollow nanoreactors dictates pathway-selective radical chemistry for rapid water decontamination

This work unveils the pivotal role of curvature-induced electronic asymmetry of the carbon shell in governing radical chemistry during peroxymonosulfate (PMS) activation within hollow nanoreactors. By selectively anchoring Co 3 O 4 nanoparticles on the inner or outer surface of mesoporous hollow carbon nanospheres (Co 3 O 4 -in/out-MHCN), we isolate two chemically equivalent but electronically distinct catalytic interfaces. Spectroscopy and density functional theory calculations reveal that curvature-induced lattice strain redistributes π-electron density outward, producing an electron-rich exterior that favors free radicals and singlet oxygen, while an electron-deficient interior stabilizes long-lived surface-bound radicals. This inward-directed asymmetry, synergizing with confinement-enhanced reactant enrichment, yields a 13.7-fold higher degradation rate constant for Co 3 O 4 -in-MHCN/PMS than for Co 3 O 4 -out-MHCN/PMS, and granular Co 3 O 4 -in-MHCN sustains continuous and biocompatible operation in a fluidized-bed reactor for 240 h. Curvature-induced electronic asymmetry thus emerges as a general design principle for steering reactive-species generation in hollow catalysts, advancing nanoconfined catalysis with high efficiency and more selective water purification.