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Copper oxides activate peroxymonosulfate for degradation of methylene blue via radical and nonradical pathways: surface structure and mechanism

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Abstract

A one-step hydrothermal method for preparation of copper oxides with different valences using ascorbic acid as a reducing reagent was developed for environmental remediation. The results suggested that the notable degradation performance of CuO0 may be attributable to the abundant active sites, such as Cu or Cu–O, and was not significantly related to the Cu valence state. In contrast to direct degradation of pollutants by traditional superoxide radicals (O2•−), O2•− played an important role in the reduction of high-valence Cu ions (Cu(III)). In addition, a series of radical quenching, electron paramagnetic resonance (EPR), and electrochemical experiments validated the existence of direct electron transfer between methylene blue (MB) and PMS mediated by CuO0 and surface-bound radicals. The results suggested that the CuO0/PMS system may be less susceptible to diverse ions and natural organic matter other than dihydrogen phosphate anions. The mechanism of MB degradation under alkaline conditions was different from that under acidic conditions in that it was not reliant on radicals or charge transfer but direct oxidation by PMS. This study provides new insights into the heterogeneous processes involved in PMS activation by the copper oxides. Furthermore, this paper devotes to providing theoretical basis on pollutant removal via PMS activated by copper oxides and developing low-cost and high-efficiency catalysts.

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All data generated or analyzed during this study are included in this published article.

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Funding

This work was supported by National Military Standard Research Project of China (20CH0612) and Dazhangxing Project of Naval Medical Center of PLA (21M0601).

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Authors and Affiliations

  1. Research Center of Water Treatment and Desalination, Naval Medical Center of PLA, Second Military Medical University, Shanghai, 200433, China

    Xu Zuo, Shiyang Zou, Junrong Wu & Bingquan Ding

  2. Naval Medical Center of PLA, Second Military Medical University, Shanghai, 200433, China

    Aijun Jiang

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  1. Xu Zuo
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  2. Aijun Jiang
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  3. Shiyang Zou
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  4. Junrong Wu
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  5. Bingquan Ding
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Contributions

Xu Zuo: Conceptualization, Investigation, Writing—original draft. Aijun Jiang: Methodology. Shiyang Zou: Editing & Supervision. Junrong Wu: Supervision. Bingquan Ding: Investigation.

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Correspondence to Shiyang Zou.

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Highlights

• Abundant active sites, such as Cu or Cu–O played a more important role in MB degradation rather than Cu valence.

• O2•− not degrading MB but involved in reduction of high valence Cu.

• Surface-bound radicals and charge transfer mediated by CuO0 was responsible for MB removal.

• Degradation of MB under alkaline was not reliant on radicals or charge transfer but direct oxidation by PMS.

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Zuo, X., Jiang, A., Zou, S. et al. Copper oxides activate peroxymonosulfate for degradation of methylene blue via radical and nonradical pathways: surface structure and mechanism. Environ Sci Pollut Res 30, 13023–13038 (2023). https://doi.org/10.1007/s11356-022-23024-6

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