Adsorption and Fenton-like Degradation of Ciprofloxacin Using Corncob Biochar-Based Magnetic Iron–Copper Bimetallic Nanomaterial in Aqueous Solutions

An economical corncob biochar-based magnetic iron-copper bimetallic nanomaterial (marked as MBC) was successfully synthesized and optimized through a co-precipitation and pyrolysis method. It was successfully used to activate H2O2 to remove ciprofloxacin (CIP) from aqueous solutions. This material had high catalytic activity and structural stability. Additionally, it had good magnetic properties, which can be easily separated from solutions. In MBC/H2O2, the removal efficiency of CIP was 93.6% within 360 min at optimal reaction conditions. The conversion of total organic carbon (TOC) reached 51.0% under the same situation. The desorption experiments concluded that adsorption and catalytic oxidation accounted for 34% and 66% on the removal efficiency of CIP, respectively. The influences of several reaction parameters were systematically evaluated on the catalytic activity of MBC. OH was proved to play a significant role in the removal of CIP through electron paramagnetic resonance (EPR) analysis and a free radical quenching experiment. Additionally, such outstanding removal efficiency can be attributed to the excellent electronic conductivity of MBC, as well as the redox cycle reaction between iron and copper ions, which achieved the continuous generation of hydroxyl radicals. Integrating HPLC-MS, ion chromatography and density functional theory (DFT) calculation results, and possible degradation of the pathways of the removal of CIP were also thoroughly discussed. These results provided a theoretical basis and technical support for the removal of CIP in water.