A state-of-art review on the redox activity of persistent free radicals in biochar

Biochar-bound persistent free radicals (biochar-PFRs) attract much attention because they can directly or indirectly mediate the transformation of contaminants in large-scale wastewater treatment processes. Despite this, a comprehensive top-down understanding of the redox activity of biochar-PFRs, particularly consumption and regeneration mechanisms, as well as challenges in redox activity assessment, is still lacking. To tackle this challenge, this review outlines the identification and determination methods of biochar-PFRs, which serve as a prerequisite for assessing the redox activity of biochar-PFRs. Recent developments concerning biochar-PFRs are discussed, with a main emphasis on the reaction mechanisms (both non-free radical and free radical pathways) and their effectiveness in removing contaminants. Importantly, the review delves into the mechanism of biochar-PFRs regeneration, triggered by metal cations, reactive oxygen species, and ultraviolet radiations. Furthermore, this review thoroughly explores the dilemma in appraising the redox activity of biochar-PFRs. Components with unpaired electrons (particular defects and metal ions) interfere with biochar-PFRs signals in electron paramagnetic resonance spectra. Scavengers and extractants of biochar-PFRs also inevitably modify the active ingredients of biochar. Based on these analyses, a practical strategy is proposed to precisely determine the redox activity of biochar-PFRs. Finally, the review concludes by presenting current gaps in knowledge and offering suggestions for future research. This comprehensive examination aims to provide new and significant insights into the redox activity of biochar-PFRs.