Metal-free catalysts with local fluorination regulation for peroxymonosulfate activation: Nearly 100 % singlet oxygen production for selective degradation of aqueous organic pollutants

Abstract

Generating singlet oxygen (1O2) via activating peroxymonosulfate (PMS) is crucial for the selective removal of organic pollutants in aquatic environments. However, achieving efficient and selective conversion of PMS into 1O2 without consuming energy or metals remains a significant challenge. In this study, graphite phase carbon nitride (g-C3N4) was locally fluorinated via a simple polymerization method. The local fluorinated g-C3N4 (FCN) was used as a metal-free catalyst to activate PMS, enabling highly efficient degradation of 4-chlorophenol (100 %) and detoxification. The FCN/PMS system demonstrates exceptional selectivity for electron-rich pollutants, functions effectively across a broad pH range (2–10), and exhibits remarkable interference resistances to background scavenging ions and natural organic compounds. Furthermore, quenching experiments, probe tests, electron paramagnetic spin resonance measurements, electrochemical characterizations, and theoretical calculations demonstrated that 1O2 was the only reactive species in the catalytic process. Local fluorination regulated the electronic structure of g-C3N4, juxtaposing electron-rich fluorine with electron-deficient carbon dual active sites. This modification alters the electron transfer direction between PMS and g-C3N4, allowing for nearly 100 % selective generation of 1O2via dual electron transfer channels without the need for energy or metals. This study provides a new strategy for designing metal-free heterogeneous catalysts to selectively generate 1O2 in a green way and can facilitate the wider applications of advanced oxidation processes for water purification.