Overcoming hydroxyl radical quenching in high-salinity wastewater: Electrostatically shielded porous perovskite boosts adsorption-oxidation of organic contaminants

IF 9.8 1区工程技术 Q1 ENGINEERING, CHEMICAL

Desalination Pub Date : 2025-09-28 DOI:10.1016/j.desal.2025.119449

Chao Li , Zaixing Li , Xueqing Xu , Hong Mo , Haitang Wang , Jiaxuan Deng , Shenghuan Liu , Yunzhi Qian , Mengfei Liu , Shilong He , Haijiao Xie

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Abstract

Free radicals are severely quenched by ubiquitous anions (e.g., Cl⁻) in high-salinity organic wastewater, which severely impedes the application of advanced oxidation processes. To address this, a free radical protection microzone (FRPM) is created on a catalyst through synergistic electrostatic repulsion (between the anionic group and anion) and physical adsorption. Specifically, poly (sodium 4-styrenesulfonate) was used to modify three-dimensionally ordered macroporous perovskite-ceria composite to introduce a surface negative layer, where anions are difficult to enter due to electrostatically repelled by the sulfonic acid group (-SO₃⁻) and avoid free radical quenching. Porous perovskites with large specific surface area and strong adsorption capacity enrich organic pollutants in FRPM through physical adsorption process and remove them by free radicals. The anionic porous perovskite composite (A-3DLFC) can completely remove tetracycline (TC) within 30 min with the k value over 0.1664 min⁻¹ in a variety of high-salinity environments. Quenching experiments and EPR tests showed that surface-bounded hydroxyl radical (·OH) is the main reactive oxygen species. Crucially, density functional theory (DFT) calculations quantitatively substantiate the FRPM mechanism, revealing an exceptionally high energy barrier (+8.19 eV) for the quenching reaction between Cl⁻ and ·OH on the A-3DLFC surface, with the Cl⁻ adsorption process being the primary limiting step (+7.09 eV).

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克服高盐度废水中的羟基自由基猝灭：静电屏蔽多孔钙钛矿促进有机污染物的吸附氧化

在高盐度有机废水中，自由基被普遍存在的阴离子（如Cl−）严重猝灭，这严重阻碍了高级氧化工艺的应用。为了解决这个问题，自由基保护微区（FRPM）是通过协同静电排斥（阴离子基团和阴离子之间）和物理吸附在催化剂上产生的。具体来说，利用聚（4-苯乙烯磺酸钠）对三维有序大孔钙钛矿-二氧化铈复合材料进行了改性，引入了表面负电层，由于磺酸基（-SO3−）的静电排斥，阴离子难以进入，避免了自由基的猝灭。比表面积大、吸附能力强的多孔钙钛矿通过物理吸附过程富集FRPM中的有机污染物，并通过自由基将其去除。阴离子多孔钙钛矿复合材料（a - 3dlfc）在各种高盐度环境下，可在30 min内完全去除四环素（TC）， k值大于0.1664 min−1。淬火实验和EPR实验表明，表面结合的羟基自由基（·OH）是主要的活性氧。重要的是，密度泛函理论（DFT）计算定量地证实了FRPM机理，揭示了A-3DLFC表面Cl -和·OH之间的猝灭反应具有极高的能垒（+8.19 eV），而Cl -吸附过程是主要的限制步骤（+7.09 eV）。

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来源期刊

Desalination 工程技术-工程：化工

CiteScore

14.60

自引率

20.20%

发文量

619

审稿时长

41 days

期刊介绍： Desalination is a scholarly journal that focuses on the field of desalination materials, processes, and associated technologies. It encompasses a wide range of disciplines and aims to publish exceptional papers in this area. The journal invites submissions that explicitly revolve around water desalting and its applications to various sources such as seawater, groundwater, and wastewater. It particularly encourages research on diverse desalination methods including thermal, membrane, sorption, and hybrid processes. By providing a platform for innovative studies, Desalination aims to advance the understanding and development of desalination technologies, promoting sustainable solutions for water scarcity challenges.