Biochar cathode: Reinforcing electro-Fenton pathway against four-electron reduction by controlled carbonization and...

Porous biochars have attracted tremendous interests in electrochemical applications. In this study, a family of biochars were prepared from cellulose subject to different carbonization temperatures ranging from 400 to 700 °C, and the biochars were in-situ activated by a molten salt (ZnCl₂) to construct a hierarchically porous architecture. The activated porous biochars (ZnBC) were used as a carbocatalyst for electro-Fenton (EF) oxidation of organic contaminants. Results showed that high-temperature carbonization improved the activity of biochar for four-electron oxygen reduction reaction (ORR) due to the rich carbon defects, while the mild-temperature treatment regulated the species and distribution of oxygen functional groups to increase the production of hydrogen peroxide (H₂O₂) via a selective two-electron ORR pathway. ZnBC-550 was the best cathode material with a high ORR activity without compromise in H₂O₂ selectivity; a high production rate of H₂O₂ (796.1 mg/g/h) was attained at -0.25 V vs RHE at pH of 1. Furthermore, Fe(II) addition induced an electro-Fenton system to attain fast decomposition of various organic pollutants at -0.25 V vs RHE (reversible hydrogen electrode) and pH of 3 with a satisfactory mineralization efficiency toward phenolic pollutants. The EF system maintains its excellent stability for 10 cycles. Hydroxyl radicals were identified as the dominant reactive oxygen species based on in situ electron paramagnetic resonance (EPR) analysis and radical quenching tests. This study gains new insights into electrocatalytic H₂O₂ production over porous biochars and provides a low-cost, robust and high-performance electro-Fenton cathode for wastewater purification.