Defect-driven Electron transfer activation of persulfate over N-doped graphene aerogels for naproxen degradation.
Liu Yu Y, Zhao Ying Y, Wang Jun J, Shen Yi Y et al.
Defect-driven catalysis has emerged as a promising paradigm for persulfate activation, yet the precise role of carbon defects relative to nitrogen dopants remains poorly understood. Herein, we synthesized nitrogen-doped graphene aerogels (NGA) with systematically tailored defect densities and nitrogen configurations via controlled pyrolysis temperatures and durations. Using naproxen (NPX) as a model pollutant, we demonstrate that the defect-engineered catalysts activate both peroxymonosulfate (PMS) and peroxydisulfate (PDS) effectively through an electron-transfer process (ETP), as verified by quenching experiments, electron paramagnetic resonance (EPR) spectroscopy, electrochemical analysis, and in-situ Raman spectroscopy. Quantitative structure-activity relationship analyses revealed that in-plane lattice disruptions (vacancies and topological defects), rather than edge sites, oxygenated functionalities, or graphitic nitrogen, serve as the primary active sites governing catalytic kinetics. Notably, PMS activation showed a stronger association with localized sp3-hybridized defective domains, whereas PDS activation exhibited a greater dependence on overall defect density, revealing distinct oxidant-dependent site preferences arising from their molecular asymmetry and electrophilicity. The optimized catalyst demonstrated excellent stability, broad pH adaptability in the PMS system (pH 3-11), resistance to real water matrices, and effective detoxification. This work resolves the ambiguity regarding active sites in nitrogen-doped carbocatalysts and provides a mechanistic framework for rational catalyst design.