Highly effective degradation of ibuprofen by alkaline metal-doped copper oxides via peroxymonosulfate activation: Mechanisms, degradation pathway and toxicity assessments

Redox ratios of Cu²⁺/Cu⁺ and adsorbed oxygen species (O_ads) have shown great activity toward radical generation by activating peroxymonosulfate (PMS). Herein, different alkaline metal oxides (CaO, MgO and BaO) and various amounts of CaO are incorporated into CuO, which could tune the main active sites of redox ratios of Cu²⁺/Cu⁺ and O_ads. The results show that CaO-CuO-5% exhibits the outstanding performance of PMS activation toward ibuprofen (IBF) degradation with excellent kinetics (k = 0.812 min⁻¹). The X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculation show that the CaO-CuO-5% has the higher electron density with superior electron transfer ability and lower PMS adsorption energy. Based on radical scavengers and electron paramagnetic resonance spectrometer (EPR), a nonradical process is proposed to play the dominant role. The degradation pathway and the corresponding toxicity of degraded intermediates with residue PMS after reaction is evaluated by LC-MS/MS and bioassay experiments, indicating the lower antagonistic influence on human hormone receptors after advanced oxidation process. Mitigation of the Cu leaching with cyclic stability can be achieved. This study provides a facile method to optimize high-performance catalysts to activate PMS and offer practical environmental applications in the remediation of emerging contaminants.