Regulating the concentration of dissolved oxygen to achieve the directional transformation of reactive oxygen species: A controllable oxidation process for ciprofloxacin degradation by calcined CuCoFe-LDH

Abstract

Different reactive oxygen species (ROS) tend to attack specific sites on pollutants, leading to the formation of intermediates with different toxic effects. Therefore, regulating the directional transformation of ROS is a new effective approach for safe degradation of refractory organic compounds in wastewater. However, the regulation mechanism and transformation path of ROS remain unclear. In this work, the dissolved oxygen (DO) content was controlled by aeration to generate different ROS through the activation of O2 on the calcined CuCoFe-LDH (CuCoFe-300). ROS quantitative experiments and electron paramagnetic resonance proved that O2 was mainly activated to superoxide radical (•O2−) and singlet oxygen (1O2) under low DO concentration (0.231 mmol/L) (O2 → •O2− → 1O2). With the increasing of DO concentration (0.606 mmol/L), O2 was inclined to convert into hydroxyl radicals (•OH) (O2 → •O2− → H2O2 → •OH). The density functional theory and function model of active sites utilization and DO concentration built a solid proof for ROS conversion mechanism that increasing the DO concentration promotes the increase of active sites utilization on the CuCoFe-300 system. That is, the •O2− was more prone to convert to •OH, not 1O2 in thermodynamics under high active sites utilization condition. Hence, the ROS generation was controlled by regulating DO concentration, and the nontoxic degradation pathway of ciprofloxacin was well-designed. This work is dedicated to the in-depth exploration of the mechanism between DO concentration and ROS conversion, which provides an extremely flexible, low energy consumption, and environmentally friendly wastewater treatment method in a new perspective.