Radical and non-radical cooperative degradation in metal-free electro-Fenton based on nitrogen self-doped biochar

To achieve sustainable metal-free electron-Fenton, N self-doped biochar air-cathode (BCAC) was prepared by pyrolyzing coffee residues. During the pyrolysis process, the endogenous N transformed from edge-doping to graphite-doping. Particularly, N vacancies started to evolve when the peak temperature exceeded 700 °C. A high Tetracycline removal rate of 70.42% was obtained on the BCAC at the current density of 4 mA cm⁻². Quenching tests incorporated with ESR spectroscopy were adopted to identify the specific oxidants produced on the cathode. The results showed that •OH (37.36%), •O₂^- (29.67%) and ¹O₂ (24.17%) played comparable role in the tetracycline removal, suggesting the coexist of radical and non-radical oxidants in our electro-Fenton system. According to the structure characterization and the DFT calculation, graphitic N was suggested as the critical site for H₂O₂ generation, and both graphitic N and pyridinic N were electroactive sites for H₂O₂ activation to •OH. Graphitic N and N vacancies with stronger capabilities in O₂ adsorption and electron-trapping were proposed as the electroactive sites for ¹O₂ and •O₂^- formation. This work predicts a novel electro-Fenton process with cooperative radical and non-radical degradation on N self-doped carbonaceous catalysts at a mild condition, which is extremely meaningful for boosting sustainable electro-Fenton technology.