Abstract
Catalytic ozonation with supported metal oxides is a promising strategy for addressing refractory pollutants in wastewater. In this study, γ-Al2O3 supported MnOx-CeOx catalysts (MC1, MC2, and MC3) obtained at different calcination temperatures (400 °C, 550 °C, and 700 °C) were applied as effective catalysts for ozonation and explored the feasibility of the treatment of oxytetracycline (OTC) wastewater. Comparatively, the MC2 possessed the highest molar ratios of Mn3+/Mn4+ (1.60) and Ce3+/Ce4+ (0.96), the largest surface area (273.8 m2 g−1) with a petal-shaped structure, and most abundant surface hydroxyls (3.78 mmol g−1). These physicochemical characteristics benefited the surface reaction and resulted in the acceleration of ozone decomposition, electron transfer, and •OH generation, thereby improving the catalyst’s adsorption ability and catalytic activity. The combination with MC2 increased the OTC and COD removal of the ozonation process from 59.1% and 29.0% to 94.7% and 83.3% in 25 min, respectively. By employing electron paramagnetic resonance (EPR) and radical quenching experiments, it was verified that •OH species generation promoted the mineralization of OTC. The possible degradation pathways of OTC were investigated through mass spectrometry, and the route consisted of dehydration, deamination, and demethylation. Moreover, during a 12-day continuous experiment, MC2 catalyst exhibited excellent reusability and catalytic stability, with COD removal efficiencies above 80%.
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The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.
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Acknowledgements
The authors are very thankful for the financial support from Ministry of Science and Technology of China and Science and Technology Department of Shandong Province.
Funding
This work was carried out with the support of the International Cooperation on Science and Technology Innovation among Governments (2019YFE0110900) and Key Technology Research and Development Program of Shandong (2019JZZY020308).
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Xinpeng Shu performed experiment, analyzed and interpreted data, wrote the original draft and wrote, and revised and edited the final manuscript. Huaqi Bi and Jun Wang performed the experiment and methodology, analyzed and interpreted data, and wrote and revised the manuscript. Jiaxin Yang performed the methodology and analyzed and interpreted data. Jue Wang helped perform the methodology and analyzed and interpreted data. Guangqing Liu provided ideas and resources for the experiment; supervised the experiment process; reviewed the manuscript. Bensheng Su directed the research, acquired funding, and revised and edited the final manuscript. All authors read and approved the final manuscript.
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Highlights
• MnOx-CeOx/γ-Al2O3 prepared at 550 °C shows improved catalytic ozonation ability.
• The higher proportion of Mn3+ and Ce3+ promotes the production of •OH.
• The ozone index of ozone/MC2 process was about 2.50 with the COD removal of 83.33%.
• Oxytetracycline removal by catalytic ozonation involves multi-adsorption/oxidation.
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Shu, X., Bi, H., Wang, J. et al. Highly stable and efficient calcined γ-Al2O3 catalysts loaded with MnOx-CeOx for the ozonation of oxytetracycline. Environ Sci Pollut Res 29, 80399–80410 (2022). https://doi.org/10.1007/s11356-022-21355-y
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DOI: https://doi.org/10.1007/s11356-022-21355-y