American Chemical Society
es3c00022_si_002.pdf (2.86 MB)

Neglected but Efficient Electron Utilization Driven by Biochar-Coactivated Phenols and Peroxydisulfate: Polyphenol Accumulation Rather than Mineralization

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journal contribution
posted on 2023-03-18, 13:03 authored by Jibo Dou, Yao Tang, Zhijiang Lu, Guangzhi He, Jianming Xu, Yan He
We report an unrecognized but efficient nonradical mechanism in biochar-activated peroxydisulfate (PDS) systems. Combining a newly developed fluorescence trapper of reactive oxygen species with steady-state concentration calculations, we showed that raising pyrolysis temperatures of biochar (BC) from 400 to 800 °C remarkably enhanced trichlorophenol degradation but inhibited the catalytic production of radicals (SO4•– and OH) in water and soil, thereby switching a radical-based activation into an electron-transfer-dominated nonradical pathway (contribution increased from 12.9 to 76.9%). Distinct from previously reported PDS* complex-determined oxidation, in situ Raman and electrochemical results of this study demonstrated that the simultaneous activation of phenols and PDS on the biochar surface triggers the potential difference-driven electron transfer. The formed phenoxy radicals subsequently undergo coupling and polymerization reactions to generate dimeric and oligomeric intermediates, which are eventually accumulated on the biochar surface and removed. Such a unique nonmineralizing oxidation achieved an ultrahigh electron utilization efficiency (ephenols/ePDS) of 182%. Through biochar molecular modeling and theoretical calculations, we highlighted the critical role of graphitic domains rather than redox-active moieties in lowering band-gap energy to facilitate electron transfer. Our work provides insights into outstanding contradictions and controversies related to nonradical oxidation and inspiration for more oxidant-saving remediation technologies.