College of Hydraulic & Environmental Engineering, China Three Gorges University, Yichang 443002, China; Engineering Research Center of Eco-environment in Three Gorges Reservoir Region, Ministry of Education, China Three Gorges University, Yichang 443002, China.
College of Hydraulic & Environmental Engineering, China Three Gorges University, Yichang 443002, China; Engineering Research Center of Eco-environment in Three Gorges Reservoir Region, Ministry of Education, China Three Gorges University, Yichang 443002, China.
J Hazard Mater. 2024 Sep 5;476:135068. doi: 10.1016/j.jhazmat.2024.135068. Epub 2024 Jul 2.
Iron-based catalysts for peroxymonosulfate (PMS) activation hold considerable potential in water treatment. However, the slow conversion of Fe(III) to Fe(II) restricts its large-scale application. Herein, an iron phosphate tungsten boride composite (FePO/WB) was synthesized by a simple hydrothermal method to facilitate the Fe(III)/Fe(II) redox cycle and realize the efficient degradation of neonicotinoid insecticides (NEOs). Based on electron paramagnetic resonance (EPR) characterization, scavenging experiments, chemical probe approaches, and quantitative tests, both radicals (HO and SO) and non-radicals (O and Fe(IV)) were produced in the FePO/WB-PMS system, with relative contributions of 3.02 %, 3.58 %, 6.24 %, and 87.16 % to the degradation of imidacloprid (IMI), respectively. Mechanistic studies revealed that tungsten boride (WB) promoted the reduction of FePO, and the generated Fe(II) dominantly activated PMS through a two-electron transfer to form Fe(IV), while a minority of Fe(II) engaged in a one-electron transfer with PMS to produce SO, HO, and O. In addition, four degradation pathways of NEOs were proposed by analyzing the byproducts using UPLC-Q-TOF-MS/MS. Besides, seed germination experiments revealed the biotoxicity of NEOs was significantly reduced after degradation via the FePO/WB-PMS system. Meanwhile, the recycling experiments and continuous flow reactor experiments showed that FePO/WB exhibited high stability. Overall, this study provided a new perspective on water remediation by Fenton-like reaction. ENVIRONMENTAL IMPLICATION: Neonicotinoids (NEOs) are a type of insecticide used widely around the world. They've been found in many aquatic environments, raising concerns about their possible negative effects on the environment and health. Iron-based catalysts for peroxymonosulfate (PMS) activation hold great promise for water purification. However, the slow conversion of Fe(III) to Fe(II) restricts its large-scale application. Herein, iron phosphate tungsten boride composite (FePO/WB) was synthesized by a simple hydrothermal method to facilitate the Fe(III)/Fe(II) redox cycle and realize the efficient degradation of NEOs. The excellent stability and reusability provided a great prospect for water remediation.
用于过一硫酸盐 (PMS) 活化的铁基催化剂在水处理中具有很大的潜力。然而，Fe(III)向 Fe(II)的缓慢转化限制了其大规模应用。在此，通过简单的水热法合成了磷酸铁钨硼复合（FePO/WB），以促进 Fe(III)/Fe(II)氧化还原循环并实现新烟碱类杀虫剂（NEOs）的有效降解。基于电子顺磁共振（EPR）表征、清除实验、化学探针方法和定量测试，在 FePO/WB-PMS 体系中产生了自由基（HO 和 SO）和非自由基（O 和 Fe(IV)），分别对吡虫啉（IMI）的降解有 3.02%、3.58%、6.24%和 87.16%的贡献。机理研究表明，钨硼化物（WB）促进了 FePO 的还原，生成的 Fe(II)主要通过两电子转移活化 PMS 形成 Fe(IV)，而少数 Fe(II)通过单电子转移与 PMS 反应生成 SO、HO 和 O。此外，通过分析 UPLC-Q-TOF-MS/MS 中的副产物，提出了 NEOs 的四种降解途径。此外，种子发芽实验表明，通过 FePO/WB-PMS 体系降解后，NEOs 的生物毒性显著降低。同时，回收实验和连续流反应器实验表明，FePO/WB 表现出较高的稳定性。总的来说，本研究为芬顿类反应的水修复提供了新的视角。
新烟碱类（NEOs）是一种在世界范围内广泛使用的杀虫剂。它们已在许多水生环境中被发现，这引起了人们对其可能对环境和健康造成负面影响的关注。过一硫酸盐（PMS）活化的铁基催化剂在水净化方面具有很大的应用前景。然而，Fe(III)向 Fe(II)的缓慢转化限制了其大规模应用。在此，通过简单的水热法合成了磷酸铁钨硼复合（FePO/WB），以促进 Fe(III)/Fe(II)氧化还原循环并实现新烟碱类杀虫剂（NEOs）的有效降解。其优异的稳定性和可重复使用性为水修复提供了广阔的前景。
