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增强 ZnO:TiO 混合氧化物光催化降解喹啉:操作参数优化及机理研究。

Enhancing photocatalytic degradation of quinoline by ZnO:TiO mixed oxide: Optimization of operating parameters and mechanistic study.

机构信息

Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, 247667, Uttarakhand, India.

Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, Uttarakhand, India.

出版信息

J Environ Manage. 2020 Mar 15;258:110032. doi: 10.1016/j.jenvman.2019.110032. Epub 2020 Jan 7.

Abstract

This study focuses on the photocatalytic degradation of quinoline, a recalcitrant heterocyclic nitrogenous aromatic organic compound, using the mixed oxide ZnO-TiO photo-catalyst. Photo-catalysts were synthesized by the solid-state reaction method at different calcination temperatures of 400 °C, 600 °C, and 800 °C. Different analytical methods, including Field emission scanning electron microscope, Brunauer-Emmett-Teller surface area, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy analysis were used for the catalyst characterization. The highest pore surface area of 57.9 mg was obtained for the photo-catalyst calcined at 400 °C. The effects of calcination temperature, solution pH, initial concentration, catalyst dose as well as irradiation time were studied. At the optimum condition, i.e., calcination temperature of 400 °C, pH ≈8 and catalyst dose of 2.5 gL, maximum quinoline degradation and total organic carbon (TOC) removal efficiency of ≈92% and ≈78% were obtained after 240 min for initial quinoline amount of 50 mgL. The 1, 2 and n-order kinetic models were applied to analyze the quinoline degradation rate. The photocatalytic mechanism was studied by drawing energy level diagram with the help of the band-gap structures of the ZnO and TiO, potential of the free radicals like OH and O and HOMO-LUMO energy gap of the quinoline molecule. The proposed pathways of quinoline mineralization were suggested on the basis of the identified intermediates by the gas chromatograph-mass spectrometer analysis and scavenger study.

摘要

本研究采用混合氧化物 ZnO-TiO 光催化剂,聚焦于喹啉(一种难降解的杂环含氮芳香有机化合物)的光催化降解。光催化剂通过不同的煅烧温度(400°C、600°C 和 800°C)的固态反应法合成。采用场发射扫描电子显微镜、Brunauer-Emmett-Teller 比表面积、X 射线衍射、紫外-可见漫反射光谱、傅里叶变换红外光谱、拉曼光谱和 X 射线光电子能谱分析等多种分析方法对催化剂进行了表征。煅烧温度为 400°C 时,光催化剂的最高孔表面积为 57.9mg。考察了煅烧温度、溶液 pH 值、初始浓度、催化剂用量和辐照时间的影响。在最佳条件下,即煅烧温度为 400°C、pH 值≈8 和催化剂用量为 2.5gL,初始喹啉浓度为 50mgL 时,最大喹啉降解率和总有机碳(TOC)去除率分别达到 92%和 78%,反应时间为 240min。应用 1、2 和 n 级动力学模型分析了喹啉的降解速率。通过绘制 ZnO 和 TiO 的能带结构、自由基(如 OH 和 O)的势能以及喹啉分子的 HOMO-LUMO 能隙的能级图,研究了光催化机理。基于气相色谱-质谱分析和清除剂研究确定的中间产物,提出了喹啉矿化的可能途径。

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