N, S, and Cl tri-doped carbon boost the switching of radical to non-radical pathway in Fenton-like reactions: Synergism of N species and defects

Heteroatom doping represents a promising strategy for enhancing the generation of singlet oxygen (1O2) during the activation of peroxymonosulfate (PMS) using carbon-based catalysts; however, it remains a formidable challenge. In this study, we systematically controlled the structure of metal-free carbon-based materials by introducing different heteroatoms to investigate their efficacy in degrading organic pollutants in water via PMS activation. The results of reactive oxygen species detection showed that the dominant free radical in the four samples was different: CN (•SO4- and •OH), CNS (•O2-), CNCl (1O2), and CNClS (1O2). This led to the transformation of active species from free radicals to non-free radicals. The tri-doped carbons with nitrogen, sulfur, and chlorine (CNClS) exhibited exceptional performance in PMS activation and achieved a remarkable degradation efficiency of 95% within just 6 min for tetracycline. Moreover, a strong linear correlation was observed between the ratio of pyridine-N/graphite-N and ID/IG with the yield of 1O2, indicating that N species and defects play a crucial role in CNClS as they facilitate the transition from radical to non-radical pathways during PMS activation. These findings highlight the possibility that adjustable tri-heteroatom doping will expand the Fenton-like reaction for the treatment of actual wastewater. Currently, there is still controversy regarding the singlet oxygen (1O2) reaction active sites on the surface of carbon. Herein, we systematically controlled the structure of metal-free carbon-based materials by introducing different heteroatoms. CNClS exhibited exceptional performance in the activation of PMS for water purification. A strong linear correlation was first observed between the ratio of pyridine-N/graphite-N and ID/IG with the yield of 1O2, indicating that N species and defects play a crucial role in CNClS during PMS activation. This study provides a feasible way for the reasonable. design of a target carbon catalyst for PMS activation.