The critical impacts of pyrochar during 2,4,6-trichlorophenol photochemical remediation process: Cooperation between persistent free radicals and oxygenated functional groups

Abstract

The widespread use of polychlorophenols poses enormous environmental challenges. Biochar has the potential to accelerate the transformation of polychlorophenols. But the biochar-triggered photochemical decomposition mechanism of polychlorophenols still remains unclear. Herein, the photochemical behavior of pyrochar was comprehensively investigated in 2,4,6-trichlorophenol (TCP) remediation. Researches revealed that persistent free radicals (PFRs) and oxygenated functional groups (OFGs) on the surface of pyrochar cooperatively promoted ROS generation for TCP degradation. PFRs performed a key role of electron-donating and energy transfer in ROS conversion, especially in the activation of H₂O₂ into •OH. The hydroxyl groups of photosensitive components of pyrochar were photo-excited and provided electrons for enhanced ROS formation as well. With photogenerated ROS involved, more TCP was decomposed through dechlorination under light irradiation than that in the dark, in which ¹O₂, •OH, and •O₂^- were the dominant active species. During this process, stronger light intensities (3 W/m²) and shorter light wavelengths (400 nm) can provide more energy for the activation of PFRs and OFGs, promoting the decomposition of TCP. This work casts a new light on the environmental roles of pyrochar in the photochemical removal of polychlorophenol pollutants.

Keywords: 2,4,6-Trichlorophenol; Biochar; Oxygenated functional groups; Persistent free radicals; Pyrochar; Reactive oxygen species.