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

ABSTRACT

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.