With the heterogeneous catalysts, high-quality reactive oxygen species could be produced in the ozonation process, which might achieve an outstanding removal efficiency of antibiotics. In this study, Cu-Ce/γ-Al2O3 (CCA) catalysts were prepared by supporting Cu and Ce on spherical γ-alumina (γ-Al2O3) and used to investigate the removal mechanism of polar and nonpolar antibiotics from wastewater, with tetracycline (TC) and ciprofloxacin (CF) as representatives, respectively. Since pH has a vital effect on the degradation of antibiotics, the optimal chemical oxygen demand (COD) removal of TC and CF reached 95.76% and 97.13% at pH 4.5 and 6.5 within 50 min, respectively, compared with only 29.36% and 28.00% removal with ozonation alone. The results of X-ray photoelectron spectroscopy spectra of CCA before and after ozonation verified that both metals (Cu and Ce) were involved in the electron transfer of the reaction system, which helped to improve catalytic efficiency. With the assistance of the hydroxyl radical (•OH) quenching experiments, it was found that the COD removal of TC was not only attributed to the adsorption assistance of CCA but mainly due to the oxidation of free •OH in solution produced by the catalysis of CCA, while the nonpolar CF was mainly removed by the oxidation of •OH adsorbed on the catalyst surface. Moreover, the repeated experiments showed that the catalyst had excellent reusability. This work clarified the removal mechanism of polar and nonpolar antibiotics in the catalytic ozonation process of composite catalysts and provided a reference for the engineering application of mineralized removal of antibiotics.
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