Effects of activated carbon, biochar, and carbon nanotubes on the heterogeneous Fenton oxidation catalyzed by pyrite for ciprofloxacin degradation

Pyrite and engineering carbon materials have received increasing attention for their catalytic potential in Fenton reactions due to their extensive sources and low cost. However, effects of carbon materials on the degradation of pollutants by pyrite-catalyzed heterogeneous Fenton oxidation have not been fully understood. In this study, the performance of pyrite-catalyzed heterogeneous Fenton system on the degradation of ciprofloxacin (CIP) was investigated in the presence of activated carbon (AC), biochar (BC), and carbon nanotubes (CNTs). Synchronous and asynchronous experiments (adsorption and catalysis) were conducted to elucidate the roles of the carbon materials in pyrite-catalyzed Fenton reactions. The results demonstrated that all the three carbon materials accelerated the pyrite-catalyzed Fenton oxidation of CIP. Under the experimental conditions, the reaction rates, which were obtained by fitting the synchronous experimental results with the pseudo-first-order kinetic model, of pyrite/AC, pyrite/BC and pyrite/CNTs with H2O2 for the removal of CIP were 8.28, 3.40 and 3.37 times faster than that of pyrite alone. Adsorption experiments and characterization analysis showed that AC had a higher adsorption capacity than BC and CNTs for CIP, which enabled it to distinguish itself in assisting the pyrite-catalyzed Fenton oxidation. In the presence of the carbon materials, the adsorption effect should not be neglected when studying the catalytic performance of pyrite. Free radical quenching experiments and electron spin-resonance spectroscopy (ESR) were used to detect and identify free radical species in the reactions. The results showed that hydroxyl radicals (•OH) contributed significantly to the degradation of CIP. The addition of carbon materials promoted the production of •OH, which favored the degradation of CIP. The results of this study suggested that the synergistic effect of oxidation and adsorption promoted the removal of CIP in pyrite/carbon materials/H2O2 systems, and coupling pyrite and carbon materials shows great potential in treating antibiotic wastewater.