Citation: Wenzheng Chen, Weiyun Chen, Bin Chen, Mingbao Feng. Deciphering the electron-shuttling role of iron(Ⅲ) porphyrin in modulating the reductive UV/S(Ⅳ) system into the oxidative strategy for micropollutant abatement[J]. Chinese Chemical Letters, ;2025, 36(10): 110743. doi: 10.1016/j.cclet.2024.110743 shu

Deciphering the electron-shuttling role of iron(Ⅲ) porphyrin in modulating the reductive UV/S(Ⅳ) system into the oxidative strategy for micropollutant abatement

Fujian Key Laboratory of Coastal Pollution Prevention and Control, College of the Environment & Ecology, Xiamen University, Xiamen 361100, China

mfeng24@xmu.edu.cn

Received Date: 16 August 2024
Revised Date: 6 November 2024
Accepted Date: 9 December 2024
Available Online: 9 December 2024

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The generation of reactive intermediates is a pivotal step during photocatalytic redox elimination of organic micropollutants in water. The UV/S(Ⅳ)-based water treatment system has garnered significant attention as an efficient advanced reduction process for pollutant abatement. However, as a reductive system, the conventional UV/S(Ⅳ) approach exhibits limited efficacy in removing electron-rich micropollutants. Our study uncovered that meso-tetrakis(4-chlorophenyl)porphyrin-Fe(Ⅲ) chloride (TPPFe, a typical iron(Ⅲ) porphyrin) catalyzed the conversion of SO₃²⁻ into SO₃^•− under UV₃₆₅ irradiation without generating of e_aq⁻ and H^•, leading to the formation of diverse oxidizing species. Additionally, the introduction of TPPFe induced an absorption redshift, broadening the range of applicable UV wavelengths. An in-depth photocatalytic cycle mechanism for TPPFe^ⅢCl−[TPPFe^ⅡCl]⁻ was introduced and verified by density functional theory (DFT) calculations. Furthermore, quantum chemistry calculations via transition state were conducted to assess the oxidizing reactivity of the reactive species with micropollutants. Both ^•OH and SO₄^•− demonstrate a strong propensity to react with carbamazepine (CMZ, a model micropollutant). Meanwhile, ¹O₂ exhibits a distinct reaction mechanism with CMZ. Consequently, the radical- and ¹O₂-mediated distinct degradation pathways were elucidated. This study provides an experimental/theoretical exploration of reactive intermediate generation and their interactions with CMZ, shedding valuable insights into the mechanisms of electron-shuttling photosensitizers catalyzing the UV/S(Ⅳ) oxidation process.
- Photocatalysis,
- Micropollutants degradation,
- Radical oxidation mechanism,
- iron(Ⅲ) porphyrin,
- DFT
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