Fragmentation-Locked Polymeric Carbon Nitride Enables Global-to-Local Electron Allocation for Enhanced Peroxymonosulfate Activation.

Developing fragmentation-locked polymeric carbon nitride with global-to-local electron allocation is crucial for enhancing its catalytic performance toward peroxymonosulfate (PMS) activation. Herein, we propose a sodium-ion-locked, iodide-induced structural memory strategy to synthesize fragmented polymeric carbon nitride (NI-PCN), which enables a continuous global-to-local electron allocation pathway for boosted PMS activation. Benefiting from this structural-electronic synergism, NI-PCN achieves 98% degradation of lornoxicam (LC) within 6 min (K = 0.5751 min-1), which is 19.3 times higher than that of pristine PCN. Experimental characterizations combined with density functional theory (DFT) calculations reveal that Na+ incorporation globally lowers the work function of the carbon nitride framework, thereby promoting long-range electron migration. Meanwhile, the cyano-rich edges formed during fragmentation and Na+ mediated electronic regulation synergistically promote local charge polarization and interfacial electron transfer to PMS molecules. This global-to-local electron allocation synergy facilitates O─O bond elongation and accelerates interfacial electron transfer, thus enabling efficient PMS activation. This work provides a new paradigm for the structural-electronic synergistic design of high-performance catalysts for PMS activation.