Electron transfer tuning for persulfate activation via the radical and non-radical pathways with biochar mediator

Electron mediator-based in-situ chemical oxidation (ISCO) offers a novel strategy for groundwater remediation due to diverse reaction pathways. However, distinguishing and further tuning the reaction pathway remains challenging. Herein, biochar as an electron mediator targeted active peroxysulphate (PDS) via the radical or non-radical pathway. Exemplified by the triazin pesticides removal, the complex radical (•OH and SO₄^•-) and non-radical active species (electron transfer oxidation) were generated and identified in different biochar/PDS systems. The electron transfer process between biochar and PDS was significantly distinguished via an innovatively in-situ visualization of radical pathway, and the electron transfer oxidation non-radical pathway is directly unveiled via a galvanic cell experiment combined with LC-MS analyses. The electron transfer mechanism was revealed via establishing the quantitative structure-activity relationships between biochar and ln k_obs. The redox capacity of biochar was assessed as a key for tuning the atrazine degradation by non-radical pathway, and the surface carbon-centered persistent free radicals (PFRs) were identified as key electron donors for triggering the radical pathway. This study gives new insights into the electron transfer mechanism during tuning radical and non-radical activation pathways and the enhanced utilization of oxidants in ISCO technology.