Atomically Dispersed Fe-Mo Catalysts Mediate Fenton-Like Reaction to Efficiently Degrade Chlorophenol Pollutants Through Synergistic Oxidation and Dechlorination Reactions

Small. 2025 Jan 15:e2410807. doi: 10.1002/smll.202410807. Online ahead of print.

Abstract

Chlorophenols are difficult to degrade and mineralize by traditional advanced oxidation processes due to the strong electronegativity of chlorine. Here, a dual-site atomically dispersed catalyst (FeMoNC) is reported, which Fe/Mo supported on mesoporous nitrogen-doped carbon is prepared through high-temperature migration. The FeMoNC exhibits a high dechlorination rate of 93.3% within 1 min. Theoretical calculation suggested that the doping of high-valence Mo6+ as the electron reservoir, promoted electronic delocalization at Fe sites, thereby enhancing the adsorption and dissociation of peroxymonosulfate (PMS), subsequent generation of Fe (IV) = O and singlet oxygen (1O2) species. An interesting finding is that Mo sites can adsorb chlorine sites in 4-chlorophenol (4-CP) and induce C─Cl bond fracture. Thus, the FeMoNC/PMS system has high catalytic performance due to the synergistic effects of Mo-induced dechlorination and non-radical species (Fe(IV) = O and 1O2) as the degradation pathways, the degradation efficiency of 99.1% of 4-CP within 5 min without significant performance decline after 168 h ≈15,120-bed volumes. These findings can advance mechanistic understanding of PMS activation at the molecular level and guide the rational design of efficient eco-friendly single-atom catalysts (SACs) catalysts with bimetallic atomic sites.

Keywords: dechlorination reaction; fenton‐like reaction; pollutants degradation; single‐atom catalysts.