A generalized surface-initiated photografting procedure, which utilizes polydopamine as a photosensitive initiating layer, allows functionalization of almost any substrate with thin polymer films under sunlight.

Achieving high specific surface area (HSSA) in graphitic carbon nitride (g-C₃N₄) severely depolymerizes the molecular chain structure, resulting in sluggish carrier kinetic behaviors and thus moderated water purification performance in photocatalytic peroxymonosulfate (PMS) activation system. Herein, we report a versatile shear-repair strategy for fabricating ultrathin porous g-C₃N₄ nanosheets with a thickness of 1.5 nm, HSSA (138.5 m² g⁻¹), and highly polymerized molecular chains. This strategy accelerates exciton dissociation and charge carrier separation, with the exciton binding energy decreasing from 65.7 to 47.5 meV. Crucially, the electron-donating pollutant and electron-withdrawing PMS generate a microelectric field at the g-C₃N₄ surface that activates PMS to generate ¹O₂ sustainably. Consequently, our catalyst exhibits an exceptional imidacloprid (IMD) removal performance with a rate constant of 0.405 min⁻¹ and remarkable PMS utilization efficiency (90% within 15 min). Moreover, under real conditions of sunlight irradiation, we observe an outstanding pollutants’ removal efficiency with a near-100% degradation rate over 20 days of continuous operation. Our work emphasizes the feasibility of synergistic molecular-level structural engineering for refining carrier kinetic behaviors in high-performance photocatalyst design.