Performance and mechanism of carbamazepine removal by FeS-S₂O₈^2– process: experimental investigation and DFT calculations

Highlights

● Synergistic removal of carbamazepine (CBZ) was obtained in the FeS-S₂O₈^2– process.

● SO₄^•− and •OH were identified as the main radicals in the FeS-S₂O₈^2– process.

● Heterogeneous oxidation would be dominant first, followed by homogeneous reaction.

● Degradation pathway of CBZ was well elucidated by experiments and DFT calculations.

Abstract

As persulfate (S₂O₈^2–) is being increasingly used as an alternative oxidizing agent, developing low-cost and eco-friendly catalysts for efficient S₂O₈^2– activation is potentially useful for the treatment of wastewater containing refractory organic pollutant. In this study, the degradative features and mechanisms of carbamazepine (CBZ) were systematically investigated in a novel FeS- S₂O₈^2– process under near-neutral conditions. The results exhibited that CBZ can be effectively eliminated by the FeS-S₂O₈^2– process and the optimal conditions were: 250 mg/L FeS, 0.5 mmol/L S₂O₈^2–, and pH = 6.0. The existence of Cl⁻ (1 and 50 mmol/L) has little influence on the CBZ elimination, while both HCO₃⁻ and HPO₄²⁻ (1 and 50 mmol/L) significantly suppressed the CBZ removal in the FeS-S₂O₈^2– process. CBZ could be degraded via a radical mechanism in the FeS-S₂O₈^2– process, the working radical species (i.e., SO₄^•− and •OH) were efficiently formed via the promoted decomposition of S₂O₈^2– by the surface Fe²⁺ on the FeS and the dissolved ferrous ions in solution. Based on the identified oxidized products and Fukui index calculations, a possible degradation pathway of CBZ was speculated. More importantly, a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S₂O₈^2– process, the activation of S₂O₈^2– by the surface-active Fe^(II) of FeS dominated in the initial 5 min, while homogeneous oxidation reactions played more essential parts than others in the following reaction stage (5–60 min). Overall, this study demonstrated that the FeS-S₂O₈^2– process is capable of removing CBZ from water efficiently.

Graphical abstract

Keywords

FeS / S₂O₈^2– / Carbamazepine / DFT calculations / Degradation routes

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Acknowledgements

The authors would like to thank the National Natural Science Foundation of China (No. 52100060), the Natural Science Foundation of Hubei Province, China (No. 2020CFB383) for the financial support.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-023-1713-1 and is accessible for authorized users.

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