Singlet oxygen-dominated non-radical oxidation pathway for 2,4-Dichlorophenol degradation over CeO₂ coated carbon fibers

Highlights

● CeO₂ was uniformly coated on the surface of carbon fibers with fibrous structure.

● ¹O₂ are generated on the active sites of Vo and C=O for CeO₂@CF.

● A large number of electron-rich oxygen vacancies formation inside CeO₂@CF.

● Complete degradation of 50 mg/L 2,4-DCP was realized with good mineralization.

● It shows good purification ability for actual coking wastewater.

Abstract

CeO₂ was uniformly coated onto the surface of carbon fibers (CF) and the resulting CeO₂@CF was employed for the activation of peroxymonosulfate (PMS) to degrade 2,4-Dichlorophenol (2,4-DCP). Under the initial conditions of a PMS concentration of 10 mmol/L, pH range of 3 to 9 and a CeO₂@CF mass concentration of 0.1 g/L, the system achieved complete degradation of 50 mg/L of 2,4-DCP with high mineralization efficiency within 60 min. Additionally, the CeO₂@CF/PMS system showed high efficiency in the presence of coexisted anions (HCO₃⁻, CO₃²⁻, SO₄²⁻, Cl⁻) and exhibited excellent purification capability for actual coking wastewater. Combined with characterization analyses (SEM-EDS, XRD, Raman, XPS, and EPR), degradation experiments and radical quenching experiments, the physicochemical properties of the prepared catalyst and the 2,4-DCP degradation mechanism were explored. Results revealed that CeO₂ was uniformly coated on the CF surface, maintaining a regular framework structure. During this process, Ce⁴⁺ in CeO₂ was reduced to Ce³⁺, resulting in numerous electron-rich oxygen vacancies forming inside CeO₂@CF. Furthermore, the CeO₂ coating increased the amount of oxygen-containing groups (C=O) on the surface of CF and graphite defects. In the CeO₂@CF/PMS system, •O₂⁻ and ¹O₂ were generated at the active sites of the oxygen vacancies (Vo) and C=O with ¹O₂ dominated non-free radical pathway and played a notable role in the 2,4-DCP degradation process.

Graphical abstract

Keywords

Carbon fiber / CeO₂ / Non-radical / 2,4-DCP / Catalytic degradation

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Acknowledgements

The authors are grateful for support by the National Natural Science Foundation of China (Nos. 22206149 and 21975172); the Fundamental Research Program of Shanxi Province (Nos. 20210302124220 and 202303021221048).

Conflict of Interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-024-1912-4 and is accessible for authorized users.

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