Revealing the generation of reactive oxygen species in hydrochar and pyrochar: Insight into rational regulation of free radicals and catalytic mechanism

Abstract

The removal of organic pollutants by biochar has been extensively studied. However, the differences in the removal mechanisms of contaminants by biochar obtained from different preparation techniques have not been thoroughly elucidated. In this study, the catalytic performances of hydrochar (HC) and pyrochar (PC) were compared in the dark and light. Owing to more persistent free radicals (PFRs), greater defects and stronger charge transfer ability on the surface, PC could produce a certain concentration of superoxide radicals (•O2−) even in the dark, making its degradation efficiency for benzoic acid (BA) 11% higher than that of HC. On the contrary, when the light was turned on, HC rather than PC can generate a higher amount of hydroxyl radical (•OH), resulting in an 11% higher degradation efficiency of BA compared to PC. The improvement of catalytic performance in HC originated from its oxygen-containing functional groups (OFGs), which was beneficial for its effective production of singlet oxygen (1O2) and ·OH under light exposure. For PC, its photocatalytic activity depended mainly on the formation of 1O2 induced by the triplet of DOM (dissolved organic matter), but the lack of oxidative ·OH in its system leads to a lower degradation efficiency than that of HC. To prove the universal applicability of this rule for biochar materials, HC and PC materials obtained from soybean residue were also prepared for degrading BA. This work is devoted to an in-depth exploration of the catalytic activation mechanism of biochar obtained by different technological methods, and can create conditions for the generation of more dominant reactive oxygen species (ROS) on biochar, thus providing the guidance for environmental remediation.