Efficient PFOA decontamination using photoelectrocatalytic coupled PMS activation: unleashing electrons and superoxide radicals for rapid degradation

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-07-08 DOI:10.1016/j.watres.2025.124182

Xiaoyue Zhang, Jun Nan, Hui Zhang, Peijie Li, Xiaoying Lin

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Abstract

Direct oxidation of per- and polyfluoroalkyl substances (PFAS) necessitates excessive energy or prolonged treatment, while reductive defluorination effectively cleaves C-F bonds. However, strict anaerobic requirements hinder its practical implementation. Herein, a photoelectrocatalytic-peroxymonosulfate (PEC-PMS) integrated system was developed for perfluorooctanoic acid (PFOA) degradation under ambient conditions. The PEC-PMS system with the sophisticated MoSe₂/TiO₂ photoelectrode demonstrated 93.6% PFOA removal within 40 minutes. Density functional theory (DFT) calculations revealed enhanced PFOA adsorption on MoSe₂/TiO₂ (E_ads = -4.25 eV) compared to TiO₂ (E_ads = -0.89 eV). Furthermore, the Mo⁴⁺/Mo⁵⁺ redox pairs promote PMS activation to accelerate reaction kinetics. The quenching experiments and electron paramagnetic resonance spectra elucidated the crucial role of electrons (63.7%) and superoxide radicals (42.2%) during the degradation. Moreover, DFT calculations and intermediate product analyses clarified the main degradation pathway of PFOA. PFOA reacted with electrons to generate C₇H₁₅· (Gibbs free energy, ΔG = -0.267 eV/mol), which was subsequently oxidized by superoxide radicals (ΔG = -4.379 eV) to form short-chain PFAS. Overall, our investigations achieved efficient PFOA elimination under air conditions and clarified their degradation mechanisms, providing a new perspective for the treatment of PFAS-contaminated wastewater.

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使用光电催化耦合PMS活化的高效PFOA去污：释放电子和超氧化物自由基以快速降解

单氟烷基和多氟烷基物质（PFAS）的直接氧化需要过多的能量或长时间的处理，而还原性脱氟可以有效地切割C-F键。然而，严格的厌氧要求阻碍了其实际实施。在此基础上，开发了一种用于环境条件下全氟辛酸（PFOA）降解的光电催化-过氧单硫酸酯（PEC-PMS）集成系统。采用先进的MoSe2/TiO2光电极的PEC-PMS系统在40分钟内可去除93.6%的PFOA。密度泛函理论（DFT）计算表明，与TiO2 （Eads = -0.89 eV）相比，MoSe2/TiO2 （Eads = -4.25 eV）对PFOA的吸附增强。此外，Mo4+/Mo5+氧化还原对促进PMS活化，加速反应动力学。淬火实验和电子顺磁共振谱分析表明，电子（63.7%）和超氧自由基（42.2%）在降解过程中起着至关重要的作用。DFT计算和中间产物分析明确了PFOA的主要降解途径。PFOA与电子反应生成C7H15·（Gibbs自由能，ΔG = -0.267 eV/mol），随后被超氧自由基（ΔG = -4.379 eV）氧化生成短链PFAS。总的来说，我们的研究在空气条件下实现了PFOA的高效去除，并阐明了其降解机制，为PFOA污染废水的处理提供了新的视角。

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来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

期刊介绍： Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include: •Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management; •Urban hydrology including sewer systems, stormwater management, and green infrastructure; •Drinking water treatment and distribution; •Potable and non-potable water reuse; •Sanitation, public health, and risk assessment; •Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions; •Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment; •Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution; •Environmental restoration, linked to surface water, groundwater and groundwater remediation; •Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts; •Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle; •Socio-economic, policy, and regulations studies.