Superoxide radical mediated Mn(III) formation is the key process in the activation of peroxymonosulfate (PMS) by Mn-incorporated bacterial-derived biochar.

Biochar was used as a heterogeneous activator for peroxymonosulfate (PMS), and the activation performance strongly depended on the structure, functional groups, and modification of the biochar. In this study, a new type of modified biochar was synthesized by utilizing the Mn(II) adsorption capacity of bacteria. After one-step pyrolysis of Mn(II)-adsorbed bacterial cells at 800 °C, a Mn-incorporated bacterial-derived biochar (Mn-BBC) was successfully produced. It exhibited structural heterogeneity, with MnO located at the surface of the BBC matrix, as shown on the result of SEM and XRD. Compared to BBC, Mn-BBC showed a 10-fold increase (0.0727 min-1 versus 0.0069 min-1) of pollutant removal rate. In addition, it also showed anti-interference capacity against common water matrix (except 10 mM CO32-) and great stability/reusability. Chemical quenching, electron spin resonance, and pyrophosphate trapping indicated an indirect but important role of the superoxide, formed during the self-decomposition of PMS. The MnO on Mn-BBC can be oxidized by superoxide to produce surface Mn(III), which then binds to PMS and forms a surface complex. This complex promotes electron transfer from the pollutant to the Mn-BBC, facilitating the oxidation of the contaminants. Overall, this study confirmed the PMS activation capacity and mechanism of Mn-BBC, which expands the application of BBC-based materials derived from metal-adsorbed microbes.