Improving the Fenton-like catalytic performance of MnO_x-Fe₃O₄/biochar using reducing agents: A comparative study

In this work, a Fenton-like system with MnO_x-Fe₃O₄/biochar composite (FeMn/biochar) and reducing agents (RAs) was constructed for pollutant degradation, aiming to enhance Fenton-like performance from both degradation efficacy and operational cost aspects. Batch experiments revealed that five well-characterized RAs (sodium borohydride (SBH), sodium thiosulfate (STS), ascorbic acid (AA), hydroxylamine (HA) and oxalic acid (OA)) could impact performance of FeMn/biochar-H₂O₂ system through multiple mechanisms, including variation of solution pH, competition for H₂O₂, electrostatic attraction and acceleration of metal redox cycle. Significantly, only OA and HA obviously enhanced the catalytic capacity of Fenton-like process and HA increased ciprofloxacin degradation efficiency from 38.2% to 92.8% with a low economic consumption as 4.16 US$/m³, well in agreement with the accelerated Fe(III/II) cycle and Mn(III/II) cycle in FeMn/biochar-H₂O₂-HA system. The accelerated metal redox cycle could enhance the decomposition of H₂O₂ into •OH and •O₂^-, which were verified to be the main reactive oxygen species responsible for ciprofloxacin degradation by radical trapping experiments. Meanwhile, FeMn/biochar-H₂O₂-HA system could also work effectively in real wastewaters, and exhibited favorable catalytic performance towards oxytetracycline, tetracycline, methyl orange, methylene blue, Rhodamine B, and naphthalene, indicating the applicability of FeMn/biochar-H₂O₂-HA system in oxidizing refractory pollutants in wastewaters.