FePO/WB as an efficient heterogeneous Fenton-like catalyst for rapid removal of neonicotinoid insecticides: ROS quantification, mechanistic insights and degradation pathways.

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.