中文题名: | 基于钛基TiO2纳米管阵列电极的水中脂多糖处理技术研究 |
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保密级别: | 公开 |
论文语种: | 中文 |
学科代码: | 083002 |
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学生类型: | 硕士 |
学位: | 工学硕士 |
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学位年度: | 2018 |
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研究方向: | 电化学水污染处理 |
第一导师姓名: | |
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提交日期: | 2018-06-07 |
答辩日期: | 2018-05-23 |
外文题名: | Study on Electrocatalytic Oxidation Treatment of Lipopolysaccharide in Aqueous Environment using Reduced Titania Nanotube Electrode |
中文关键词: | Reduced titania nanotube electrode ; Electrocatalytic oxidation ; Lipopolysac charide ; Endotoxin toxicity ; Acute toxicity |
中文摘要: |
脂多糖是细菌细胞壁上的物质,随着细菌死亡被释放到环境中,因此生化出水中含量通常达到5000 EU mL-1以上。高浓度的脂多糖会通过呼吸和血液进入人体内,造成发热、呼吸困难甚至休克等症状,危害人体健康。本研究以脂多糖为目标污染物,以钛基TiO2纳米管阵列电极为阳极材料,研究了不同条件下脂多糖的去除效率,并对脂多糖的降解途径和脱毒机理进行了探讨。
采用阳极氧化方法,制备得到了TiO2纳米管阵列电极,并通过阴极还原制备得到还原后的TiO2纳米管阵列电极。测试了该极板的表面形貌、晶型表征以及电化学性能,结果表明,该电极表面是由大量纳米管紧密排列构成,还原后的电极中部分TiO2被还原成Ti4O7和Ti5O9,电阻和阻抗下降。比较了还原后的TiO2纳米管阵列电极与Ti/SnO2-Sb、Ti/SnO2-Sb/PbO2和Ti/SnO2-Sb/Ce-PbO2三种电极材料对脂多糖的去除效果,结果表明,TiO2纳米管阵列电极对脂多糖去除率最高为68.5%的。考察了电流密度(0.5-6.0 mA cm-2)、极板间距(0.5-3.0 cm)、脂多糖初始浓度(10-200 mg L-1)、支持电解质种类和初始pH值(3.0-11.0)等因素对脂多糖在TiO2纳米管阵列电极上去除效果的影响。实验结果表明,提高电流密度能够提高水中多糖和TOC的去除率;初始pH值对脂多糖的去除影响较大,当初始pH值为7.0时,多糖和TOC去除率分别为99.7%和96.6%,远高于初始pH值(5.7)的去除率。
对所产生羟基自由基的产率测试表明,TiO2纳米管阵列电极为0.0062 mmol L-1 min-1,低于Ti/SnO2-Sb、Ti/SnO2-Sb/PbO2和Ti/SnO2-Sb/Ce-PbO2三种电极,其产率分别为0.0189、0.0288和0.0375 mmol L-1 min-1,在反应体系中添加三种自由基淬灭剂的结果表明,添加自由基淬灭剂对多糖的去除产生影响不显著,说明脂多糖的降解可能和极板的直接反应有关。当初始pH为7.0时,经过120 min的电催化氧化处理后,脂多糖的内毒素毒性和TOC的去除率分别为95%和98%。急性毒性实验结果表明,急性毒性在反应初期迅速升高到99%,持续约3小时,但在电解240 min后对发光细菌的抑制比仅为5%左右。通过对实验结果以及类脂A结构的最高占有分子轨道进行分析,推测TiO2纳米管阵列电极上脂多糖的去除主要是由于脂多糖的疏水性、电场力、分子扩散、极板吸附、脂多糖的水解以及电子的直接转移等共同作用的结果。
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外文摘要: |
Lipopolysaccharide(LPS) is a substance on the cell wall of bacteria, which is released into the environment with the death of bacteria. Therefore, the content of LPS usually could reach 5000 EU mL-1. The high concentration of LPS could enter the body through breathing and blood, and cause fever, syspnea and even shock. This paper studied the removal efficiency of LPS under different conditions on the reduced TiO2 nanotube arrays electrode, and discussed the degradation pathway and detoxification mechanism of LPS.
In this work, the reduced TiO2 nanotube arrays electrode was prepared by the method of anodic oxidation and cathodic reduction. The surface morphology, crystal characterization and electrochemical properties of the electrode were tested. The results showed that the surface of electrode was compactly composed of countless nanotubes, and partial TiO2 was reduced to Ti4O7 and Ti5O9, which caused decrease of the resistance and impedance. Then, the effect of the blue TNTs electrode and other three electrode materails of Ti/SnO2-Sb, Ti/SnO2-Sb/PbO2 and Ti/SnO2-Sb/Ce-PbO2 on the removal of LPS was compared, which showed that the removal rate of LPS was best (68.5%) on reduced TiO2 nanotube arrays electrode. The effects of current density (0.5-6.0 mA cm-2), plate spacing (0.5-3.0 cm), initial concentration of LPS (10-200 mg L-1), type of supporting electrolyte and initial pH value (3-11) on the removal of LPS were investigated on reduced TiO2 nanotube arrays electrode. The expetimental results showed that higher current density could increase the removal rate of LPS, polysaccharide and TOC. Besides, the initial pH value had great influence on the removal of LPS. When the initial pH value was 7.0, the removal rate of polysaccharide and TOC was 99.7% and 96.6% respectively, which was higher than the condition of original pH value (5.7).
The production of ·OH of reduced TiO2 nanotube arrays electrode was 0.0062 mmol L-1 min-1 which was lower than Ti/SnO2-Sb (0.0189 mmol L-1 min-1), Ti/SnO2-Sb/PbO2 (0.0288 mmol L-1 min-1) and Ti/SnO2-Sb/Ce-PbO2 (0.0375 mmol L-1 min-1). At the same time, three kinds of free radical quenching agents were added into the reaction system, which had little influence on the removal of polysaccharide. The result showed that the degradation of LPS was not dependent on the indirect reation of electrode. When the initial pH is 7.0, the removal rate of endotoxin toxicity and TOC was above 95% and 98% respectively after the electrocatalytic oxidation for 120 min. Acute toxicity rapidly increased to 99% in a few minutes and lasted for about 3 hours, then slowly decreased with the increase of TOC removal rate. The acute toxicity was only about 5% after electrolysis for 240 min. Through the analysis of the previous experimental results and the highest occupancy molecular orbit (HOMO) of the lipid A structure, it is speculated that the removal of LPS on the reduced TiO2 nanotube arrays electrode was the result of the joint action of hydrophobicity of LPS, electric field force, adsorption of electrode, hydrolysis of LPS and the direct electron transfer.
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参考文献总数: | 0 |
馆藏号: | 硕083002/18013 |
开放日期: | 2019-07-09 |