Coupled adsorption-photocatalysis process for the removal of diclofenac using magnetite/reduced graphene oxide nanocomposite

Abstract

Diclofenac (DCF) is frequently detected in water bodies (ng/L to g/L) as it is not completely removed by conventional wastewater treatment plants. Adsorption and photocatalysis have been studied as promising methods for treating DCF; however, both processes have limitations. Thus, in this study, the removal efficiency of DCF is evaluated using a magnetite/reduced graphene oxide (Fe3O4/RGO) nanocomposite via a coupled adsorption-catalysis process. The Fe3O4/RGO nanocomposite was successfully synthesized using a microwave-assisted solvothermal method and exhibited a bandgap of 2.60 eV. The kinetic data best fitted the Elovich model (R2 = 0.994, χ2 = 0.29), indicating rapid adsorption. The maximum DCF adsorption capacity calculated using the Langmuir model was 80.33 mg/g. An ultraviolet C (UVC) light source and 0.1 g/L of Fe3O4/RGO nanocomposite were the optimum conditions for the removal of DCF (C0 = 30 mM) by a coupled adsorption-photocatalysis process (first-order rate constant (k) = 0.088/min), which was greater than the single adsorption (k = 0.029/min) and pre-adsorption and post-photocatalysis (k = 0.053/min) processes. This indicates that the adsorbed DCF did not hamper the photocatalytic reaction of the Fe3O4/RGO nanocomposite, but rather enhanced the coupled adsorption-photocatalytic reaction. DCF removal efficiency was higher at acidic conditions (pH 4.3–5.0), because high H+ promotes the generation of certain reactive oxygen species (ROS) and increases of electrostatic interaction. The presence of NaCl and CaCl2 (10 mM) did not notably affect the total DCF removal efficiency; however, Ca2+ affected the initial DCF adsorption affinity. Scavenger experiments demonstrated O2∙− and h+ play a key ROS than ·OH to degrade DCF. The acute toxicity of DCF towards Aliivibrio fischeri gradually decreased with increasing treatment time.