n→π* Electron Transitions and Directional Charge Migration Synergistically Promoting O2 Activation and Holes Utilization on Carbon Nitride for Efficiently Photocatalytic Degradation of Organic Contaminants

Stimulating electron transitions and promoting exciton dissociation are crucial for improving the photocatalytic performance of polymeric carbon nitride (CN) yet still challenging. Herein, a novel CN with C dopant and asymmetric structure (CC-UCN2 ) is ingeniously synthesized. The obtained CC-UCN2 not only reinforces the intrinsic π→π* electron transitions, but also successfully awakens additional n→π* electron transitions. Besides, charge centers dislocation caused by symmetry breaking induces a spontaneous polarized electric field, effectively breaking the constraints of Coulomb electrostatic interaction between electrons and holes and driving their directional migration. Along with the spatial separation of reduction and oxidation sites, CC-UCN2 shows exceptional O2 activation and holes oxidation efficiency, thus exhibits a high degradation rate constant (0.201 min-1 ) and mineralization rate (80.1%) for bisphenol A (BPA)(far outperforming pristine and other modified CNs). This work proposes a novel perspective for developing high-efficiency photocatalysts and comprehending the underlying mechanism of O2 activation and holes oxidation for pollutant degradation.