Performance and mechanism of carbamazepine removal by FeS-S2O82– process: experimental investigation and DFT calculations

doi:10.1007/s11783-023-1713-1

Front. Environ. Sci. Eng.

2023, Vol. 17

Issue (9) : 113 https://doi.org/10.1007/s11783-023-1713-1

RESEARCH ARTICLE

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

Xuejun Long^1,², Jun Luo¹, Zhenxing Zhong^1,²(

), Yanxu Zhu³, Chunjie Zhang³, Jun Wan^1,², Haiyan Zhou⁴, Beiping Zhang⁵, Dongsheng Xia^1,²

¹. College of Environmental Engineering, Wuhan Textile University, Wuhan 430200, China
². Engineering Research Center for Clean Production of Textile Printing and Dyeing (Ministry of Education), Wuhan Textile University, Wuhan 430073, China
³. Central & Southern China Municipal Engineering Design and Research Institute Co., Ltd., Wuhan 430010, China
⁴. Soil Environmental Institute, Guangdong Provincial Academy of Environmental Science, Guangzhou 510045, China
⁵. School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

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Abstract

● 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.

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.

Keywords FeS S₂O₈^2– Carbamazepine DFT calculations Degradation routes

Corresponding Author(s): Zhenxing Zhong

Issue Date: 11 April 2023

Cite this article:

Xuejun Long,Jun Luo,Zhenxing Zhong, et al. Performance and mechanism of carbamazepine removal by FeS-S₂O₈^2– process: experimental investigation and DFT calculations[J]. Front. Environ. Sci. Eng., 2023, 17(9): 113.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1713-1
https://academic.hep.com.cn/fese/EN/Y2023/V17/I9/113

Fig.1 (a) Comparison of CBZ degradation in the various processes, (b) k_obs values of above four systems. (Reaction conditions: [CBZ]₀ = 10 mg/L, [FeS]₀ = 250 mg/L, [S₂O₈^2–]₀ = 0.5 mmol/L, Initial pH = 6.0, t = 25 °C).

Fig.2 Effects of different FeS contents (a), different S₂O₈^2–concentrations (b), and various initial pH (c) on the CBZ degradation by the FeS-S₂O₈^2– process; variation of CBZ degradation reaction rate constants (k_obs) under different FeS dosages (d), initial S₂O₈^2– concentrations (e), and initial pH (f). (Reaction conditions: [CBZ]₀ = 10 mg/L, t = 25 °C).

Fig.3 Effects of CBZ concentrations on the CBZ degradation by the FeS-S₂O₈^2– process (a), the profiles of S₂O₈^2– decomposition (b), and the evolutions of Fe²⁺ (c) and total Fe (d) in solution. (Reaction conditions: [FeS] = 250 mg/L, [S₂O₈^2–] = 0.5 mmol/L, initial pH = 6.0, t = 25 °C).

Fig.4 Effects of coexisting anions Cl^– (a), HPO₄^2– (b), and HCO₃^–(c) on CBZ degradation in the FeS-S₂O₈^2–process. (Reaction conditions: [CBZ]₀ = 10 mg/L, [FeS]₀ = 250 mg/L, [S₂O₈^2–]₀ = 0.5 mmol/L, initial pH = 6.0, t = 25 °C).

Fig.5 XRD spectrum of FeS before and after reaction (a), contents of Fe and S from XPS spectra before and after reaction (b), EPR (c), and effects of TBA and EtOH on the removal of CBZ (d).

Fig.6 CBZ chemical structure (a), HOMO (b) and LUMO (c) orbital distributions of CBZ, Fukui index (f⁺, f^–, and f⁰) of CBZ (d).

Fig.7 Possible degradation pathways of CBZ in the FeS-S₂O₈^2– process.

Fig.8 Proposed two-stage mechanisms of FeS-S₂O₈^2– process toward CBZ degradation.

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