Cai Chun, Shi Jiarui, Liu Qing, Zhu Qiqi, Fu Qing, Wang Wei, Duan Xiaodi
MOE Key Laboratory of Groundwater Quality and Health, School of Environmental Studies, China University of Geosciences, Wuhan 430078, China; State Environmental Protection Key Laboratory of Source Apportionment and Control of Aquatic Pollution & Hubei Provincial Engineering Research Center of Systematic Water Pollution Control, China University of Geosciences, Wuhan 430078, China.
Key Laboratory of Organic Compound Pollution Control Engineering (MOE), School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China.
J Hazard Mater. 2025 Oct 5;497:139666. doi: 10.1016/j.jhazmat.2025.139666. Epub 2025 Aug 25.
Peracetic acid (PAA)-driven advanced oxidation processes (AOPs) are increasing favored for water treatment due to their environmentally benignity and ease of activation. However, the development of low-cost and high-performance activators is still a primary challenge. In this study, Fe-doped g-CN (Fe-N-C) was fabricated as an efficient peracetic acid (PAA) activator for sustainable degradation of emerging contaminants (ECs) like bisphenol A (BPA) with a removal efficiency of 97.8 %. Quite different from the reported non-radical involved catalytic studies, Fe-N-C-PAA complex (Fe(III)-OO(O)CCH) was formed and served as the primary reactive species rather than high-valent iron-oxo species (Fe=O) and singlet oxygenation (O) for the oxidation of BPA on the basis of electron paramagnetic resonance (EPR) spectra, chemical quenching and probe tests, Raman spectroscopy, O isotope labeling tests, electrochemical analysis and density-functional theory (DFT) calculations in the Fe-N-C/PAA process. Satisfactory BPA removal efficiency can still be obtained with water matrices, in actual water, after 5 cycles of Fe-N-C, at the flow-through device with carbon felt for 120 h. BPA was successfully detoxified within 60 min and the probable degradation pathway of BPA was elucidated with the assistance of DFT calculations. The correlation between k and Hammett constants σ or half-wave potentials (φ) of different organics implied that the contaminants with greater electron-donating capacity were more prone to be oxidized. This study advances the understanding of metal-PAA complex, offering novel insights into PAA activation using multiphase iron-based catalysts and their potential for practical environmental applications.
过氧乙酸（PAA）驱动的高级氧化过程（AOPs）因其环境友好性和易于活化而越来越受到水处理领域的青睐。然而，开发低成本、高性能的活化剂仍然是一个主要挑战。在本研究中，制备了铁掺杂的石墨相氮化碳（Fe-N-C）作为一种高效的过氧乙酸（PAA）活化剂，用于可持续降解双酚A（BPA）等新兴污染物（ECs），去除效率达97.8%。与已报道的非自由基参与的催化研究截然不同，基于电子顺磁共振（EPR）光谱、化学猝灭和探针测试、拉曼光谱、O同位素标记测试、电化学分析和密度泛函理论（DFT）计算，在Fe-N-C/PAA过程中，形成了Fe-N-C-PAA络合物（Fe(III)-OO(O)CCH）并作为主要反应物种，而非高价铁氧物种（Fe=O）和单线态氧（O）用于氧化BPA。在实际水体的水基质中，经过5次Fe-N-C循环后，在装有碳毡的流通装置中运行120小时，仍可获得令人满意的BPA去除效率。BPA在60分钟内成功解毒，并借助DFT计算阐明了BPA可能的降解途径。k与不同有机物的哈米特常数σ或半波电位（φ）之间的相关性表明，供电子能力越强的污染物越容易被氧化。本研究推进了对金属-PAA络合物的理解，为使用多相铁基催化剂活化PAA及其在实际环境应用中的潜力提供了新的见解。
