Electron-transfer-based peroxymonosulfate activation on defect-rich carbon nanotubes: Understanding the substituent...

Nanocarbon-based persulfate oxidation technologies are promising for green elimination of phenolic pollutants. Previous studies revealed the electron transfer via defective carbon nanotube (CNTs) for selective oxidation of various phenols. However, an underlying relationship between the molecular structure of phenols and the selectivity of electron transfer-induced oxidation has not been well understood. Herein, we report that defect-rich CNTs could initiate electron-transfer regime from phenols to peroxymonosulfate (PMS), resulting in the efficient degradation of phenols. Further studies uncover a distinctive substituent group-dependent selective oxidation of phenols via the CNT-mediated electron transfer process. Specifically, the degradation rate of para-substituted phenols with electron-donating groups (e.g., -NH₂ and -OCH₃) is faster than those with electron-withdrawing groups (e.g., -NO₂ and -COOH). For a kind of substituted phenols, the substituent position has a great influence on the phenols degradation and their degradation rates follow this sequence: para > ortho > meta -position. Besides, increasing the number of the substituent group can accelerate the degradation of substituted phenols. This study elucidates the substituent effect on the electron transfer-dominated selective oxidation of phenols for the first time, which guides the application of carbon/persulfate system for the targeted remediation of phenols-polluted wastewater.