基于紫外LED阵列光催化降解抗生素的研究

doi:10.3964/j.issn.1000-0593(2019)09-2894-07

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摘要：抗生素的大量使用对生态环境造成巨大的影响，光催化技术具有操作简单且无二次污染等特点被广泛应用于污染物的降解。在光催化降解抗生素过程中，光源对其降解效率至关重要，与传统的汞灯催化光源相比，紫外LED技术具有更高的能源效率及更低的功耗，使光催化工艺发生了巨大的变化。首先建立基于紫外LED阵列的光催化平台，采用光栅光谱仪和紫外照度计对LED阵列光源光谱特性及装置内光场分布进行测量分析。结果显示紫外LED光源波长介于265～295 nm之间，其主波长为275 nm，由于光场叠加效果，光照强度随着装置径向位置距离的增大而明显增大，装置轴向位置光照强度分布较为均匀；其次通过三维超景深显微镜、UV-Vis光谱测量技术对P25型光催化剂的粒子结构进行表征分析，同时使用半导体求导公式对TiO₂粉末进行禁带分析，结果显示TiO₂为球形，由于空气中相对湿度过大，水在TiO₂微粒表面的润湿性加强了微粒间的粘附力，因此有团聚现象产生，其禁带宽度为3.1 eV；最后以紫外LED阵列和高压汞灯为催化光源，P25型TiO₂为催化剂分别对甲基橙、磺胺类抗生素进行光催化降解，使用紫外-可见光分光光度计测量降解过程中的吸收光谱曲线，进而对抗生素降解率进行分析。结果表明，甲基橙和磺胺二甲嘧啶在紫外LED阵列为光源条件下均能够被降解，分别经过160和240 min的催化降解过程后，降解率分别达到70%和36%，符合一级动力学方程，经计算LED阵列光源与汞灯对甲基橙的降解动力学常数分别为-0.007 5和-0.113 5 min^-1，对磺胺二甲嘧啶的降解动力学常数分别为-0.001 9和-0.019 4 min^-1。因此对甲基橙和磺胺二甲嘧啶进行降解时，汞灯降解速率高于紫外LED阵列；由于紫外LED阵列和汞灯系统在催化降解污染物过程中功率和其与反应器中轴线距离不同，对两种光源的抗生素降解效率建立评价方法，即对紫外LED和汞灯以单位功率为标准进行距离降解效率分析，对于甲基橙，汞灯在单位功率下的距离降解效率高于紫外LED，但对于抗生素，紫外LED阵列的距离降解效率明显高于汞灯。依据以上各类光谱分析和应用结果，紫外LED阵列是一种有竞争力的光催化应用替代光源，此技术的广泛应用为抗生素的降解提供新途径。

关键词：紫外LED阵列；光催化；抗生素；光谱

Abstract：The heavy use of antibiotics has caused great damage to the ecological environment. Photocatalytic technology is widely used in the degradation of pollutants because it is easy to operate and will not harm the environment again. In the process of photocatalytic degradation of antibiotics, the choice of light source is very important for the degradation efficiency of antibiotics. Compared with mercury lamps, which are usually used as photocatalytic light sources, UV-LED have higher energy efficiency and lower energy consumption. Therefore, the application of UV-LED technology has brought about huge changes in the photocatalytic process. First, this paper establishes a photocatalytic platform based on UV-LED array. The spectral characteristics of the LED array light source and the light field distribution in the device are measured and analyzed by a grating spectrometer and an UV illuminometer. The results show that the wavelength of the UV-LED source is between 265 and 295 nm, and its dominant wavelength is 275 nm. Due to the influence of the superposition of the light field, the radial intensity of the device increases significantly with the increase of the radial distance. The distribution of light intensity at the axial position is relatively uniform; Secondly, the particle structure of P25 photocatalyst is characterized by 3D microscope with super wide depth of field and UV-Vis technology. At the same time, the semiconductor derivative formula is used to analyze the band gap of P25. The results showed that the TiO₂ was spherical. Due to the excessive relative humidity in the air, the moisture on the surface of TiO₂ enhances the adhesion among particles. Therefore, the TiO₂ particles have agglomeration. And the band gap of TiO₂ is 3.1 eV. Finally, UV-LED and high pressure mercury lamp are used as the catalytic light source. Photocatalytic degradation of methyl orange (MO) and sulfonamides (SM₂) using P25 as a catalyst. Ultraviolet-visible spectrophotometer is used to measure the absorbance in the degradation process, and the degradation rate of antibiotics is further analyzed. The results showed that MO and SM₂ could be degraded under UV-LED array. After the catalytic degradation process of 160 and 240 min, the degradation rates reached 70% and 36%. It conformed to the first order kinetic equation. The degradation kinetics constants of MO by LED array light source and mercury lamp were -0.007 5 and -0.113 5 min^-1. The degradation kinetics constants of SM₂ were -0.001 9 and -0.019 4 min^-1. Therefore, the degradation rate of the mercury lamp is higher than that of UV-LED array in case of degradation analysis of MO and SM₂. In catalytic degradation of pollutants, UV-LED arrays and mercury lamp systems differ in power and in distance from the axis of the reactor, and an evaluation method for the degradation efficiency of antibiotics under two light sources was established. Distance degradation efficiency of UV-LED and mercury lamp at unit power standard was adopted in this paper. For MO, distance degradation efficiency of mercury lamp at unit power is larger than that of ultraviolet LED. For SM₂, distance degradation efficiency of the UV-LED array is larger than that of the mercury lamp. Based on the results of various spectral analysis and application above, UV-LED array is a competitive alternative to light source for photocatalytic. The widespread application of this technology provides a new way to degrade antibiotics.

Key words：UV-LED; Photocatalysis; Antibiotic; Spectrum

收稿日期: 2018-07-24 修订日期: 2018-12-05

中图分类号:

O433.4

基金资助: 国家自然科学基金项目（51675189）、广东大学生科技创新培育专项资金项目（Pdjhb0077），广州市科技计划项目（201605030013）资助

通讯作者: 杨洲，赵文锋 E-mail: zwf555@scau.edu.cn；yangzhou@scau.edu.cn

作者简介: 马立哲，1994年生，华南农业大学电子工程学院硕士研究生 e-mail：15670010927@163.com

引用本文:

马立哲，季邦，杨洲，黄权锋，赵文锋. 基于紫外LED阵列光催化降解抗生素的研究[J]. 光谱学与光谱分析, 2019, 39(09): 2894-2900.
MA Li-zhe, JI Bang, YANG Zhou, HUANG Quan-feng, ZHAO Wen-feng. Study of Photocatalytic Degradation of Antibiotics Based on UV-LED Array. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2019, 39(09): 2894-2900.

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