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一种用于多菌灵光催化降解的新型CuO/ZnO@PET复合膜

A Novel CuO/ZnO@PET Composite Membrane for the Photocatalytic Degradation of Carbendazim.

作者信息

Altynbaeva Liliya Sh, Barsbay Murat, Aimanova Nurgulim A, Jakupova Zhanar Ye, Nurpeisova Dinara T, Zdorovets Maxim V, Mashentseva Anastassiya A

机构信息

The Institute of Nuclear Physics of the Republic of Kazakhstan, Almaty 050032, Kazakhstan.

Department of Chemistry, L.N. Gumilyov Eurasian National University, Nur-Sultan 010008, Kazakhstan.

出版信息

Nanomaterials (Basel). 2022 May 18;12(10):1724. doi: 10.3390/nano12101724.

Abstract

The extremely high levels of water pollution caused by various industrial activities represent one of the most important environmental problems. Efficient techniques and advanced materials have been extensively developed for the removal of highly toxic organic pollutants, including pesticides. This study investigated the photocatalytic degradation of the fungicide carbendazim (Czm) using composite track-etched membranes (TeMs) in an aqueous solution. Copper(I) oxide (CuO) and zinc oxide (ZnO) microtubes (MTs) were prepared using an electroless template deposition technique in porous poly(ethylene terephthalate) (PET) TeMs with nanochannels with a density of 4 × 10 pores/cm and diameter of 385 ± 9 nm to yield CuO@PET and ZnO@PET composite membranes, respectively. A mixed CuO/ZnO@PET composite was prepared via a two-step deposition process, containing ZnO (87%) and CuZ (13%) as crystalline phases. The structure and composition of all composite membranes were elucidated using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques. Under UV-visible light irradiation, the CuO/ZnO@PET composite displayed enhanced photocatalytic activity, reaching 98% Czm degradation, higher than CuO@PET and ZnO@PET composites. The maximum Czm degradation efficiency from aqueous solution was obtained at an optimal pH of 6 and contact time of 140 min. The effects of various parameters such as temperature, catalyst dosage and sample exposure time on the photocatalytic degradation process were studied. The degradation reaction of Czm was found to follow the Langmuir-Hinshelwood mechanism and a pseudo-first order kinetic model. The degradation kinetics of Czm accelerated with increasing temperature, and the activation energy () levels were calculated as 11.9 kJ/mol, 14.22 kJ/mol and 15.82 kJ/mol for CuO/ZnO@PET, ZnO@PET and CuO@PET composite membranes, respectively. The reusability of the CuO/ZnO@PET catalyst was also investigated at different temperatures for 10 consecutive runs, without any activation or regeneration processes. The CuO/ZnO@PET composite exhibited degradation efficiency levels of over 50% at 14 °C and over 30% at 52 °C after 5 consecutive uses.

摘要

各种工业活动造成的极高水污染水平是最重要的环境问题之一。人们已经广泛开发了高效技术和先进材料来去除包括农药在内的剧毒有机污染物。本研究考察了在水溶液中使用复合径迹蚀刻膜(TeMs)对杀菌剂多菌灵(Czm)进行光催化降解。采用化学模板沉积技术,在密度为4×10个孔/平方厘米、直径为385±9纳米的多孔聚对苯二甲酸乙二酯(PET)纳米通道径迹蚀刻膜中制备氧化亚铜(CuO)和氧化锌(ZnO)微管(MTs),分别得到CuO@PET和ZnO@PET复合膜。通过两步沉积法制备了混合的CuO/ZnO@PET复合材料,其结晶相包含87%的ZnO和13%的CuZ。使用扫描电子显微镜(SEM)、原子力显微镜(AFM)、能量色散X射线光谱(EDS)、X射线光电子能谱(XPS)和X射线衍射(XRD)技术对所有复合膜的结构和组成进行了阐明。在紫外-可见光照射下,CuO/ZnO@PET复合材料表现出增强的光催化活性,Czm降解率达到98%,高于CuO@PET和ZnO@PET复合材料。在最佳pH值为6和接触时间为140分钟时,从水溶液中获得了最大的Czm降解效率。研究了温度、催化剂用量和样品暴露时间等各种参数对光催化降解过程的影响。发现Czm的降解反应遵循Langmuir-Hinshelwood机理和准一级动力学模型。Czm的降解动力学随温度升高而加快,CuO/ZnO@PET、ZnO@PET和CuO@PET复合膜的活化能()水平分别计算为11.9 kJ/mol、14.22 kJ/mol和15.82 kJ/mol。还在不同温度下连续10次运行研究了CuO/ZnO@PET催化剂的可重复使用性,无需任何活化或再生过程。连续使用5次后,CuO/ZnO@PET复合材料在14℃时降解效率水平超过50%,在52℃时超过30%。

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