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TiO2基纳米管阵列用于光催化降解车内TVOC的基础研究

Basic Study on Photocatalytic Degradation of Car TVOC by the TiO2Based Nanotube Arrays

【作者】 王敏

【导师】 贾力;

【作者基本信息】 北京交通大学 , 载运工具运用工程, 2014, 博士

【摘要】 由于当前汽车内部TVOC严重危害人体健康。本论文以光催化技术在环境领域的广泛应用为背景,从分析汽车内饰材料释放TVOC及光催化技术的特点出发,通过搭建TVOC释放、阳极氧化及光催化降解TVOC实验台,研究了汽车内饰材料释放的TVOC的特征及TiO2基纳米管阵列光催化材料的制备工艺,并通过建立TiO2基纳米管阵列降解TVOC的数理模型,来揭示TVOC降解速率与光催化工艺参数的定量关系。实验研究发现TVOC释放系数随温度的升高、湿度的增加而升高;选择了三种预处理方法对纤维类内饰材料的TVOC作了去除效果研究,结果显示,三种预处理方法均能有效去除脚垫中TVOC,其中水洗风干法效果最好,且水洗温度越高,效果越好。利用阳极氧化法制备了TNAs并进行表征,结果显示,纳米管的形貌与溶剂有关,具有合适粘度及电导率的乙二醇适宜于作阳极氧化制备TNAs的溶剂;阳极面积过大或过小时,不能生成纳米管或生成后很快破裂,当极液比为0.05cm-1时,能生成形貌较好的TNAs;电极间距适中时,本研究条件下,电极间距为2cm时,形成垂直于钛片表面的规则排列的TNAs。基于TVOC分子在纳米管内的质量传递原理,建立了TANs用于光催化降解TVOC的反应速率数理模型,通过实验估计了模型参数,并将模型预测结果与实验数据对比,吻合较好,误差在±20%以内。模型结果表明:存在最优管径,使降解速率达到最大。实验研究了光催化活性较好的Fe2O3/TiO2、Cu2O/TNAs复合纳米管的制备工艺,分析了二者的形貌、光响应程度及对模拟车内TVOC气体的降解效果,发现降解效果的提高程度与Cu2O、Fe2O3的掺入量有关,Cu2O/TNAs复合纳米管的降解效果优于Fe2O3/TNAs;二者对TVOC的降解符合一级反应规律。实验研究了Cu2O/TNAs中含Cu量、反应温度、混合气体的湿度及含氧量对TVOC光催化降解的影响,建立了Cu2O/TNAs光催化降解TVOC的动力学模型,并将模型预测结果与实验数据对比,误差在±20%以内。模型显示Cu2O/TNAs催化降解该类TVOC的最佳催化剂含Cu量为31.37%,最佳含氧量为36.92%,最佳湿度为33.71%。

【Abstract】 As is known to us all, automotive interior materials release lots of volatile organic compounds(VOC), which harm human health seriously. This paper outlines the TVOC emission from interior materials and the wide application of photocatalytic purification technology in the environment field. By setting up TVOC emission measuring bench and photocatalytic TVOC degradation bench, We studied the TVOC emission characteristic from interior materials and the preparation process of TiO2-based nanotube arrays, and established the mathematical medol of TVOC photocatalytic degradation on TiO2-based nanotube arrays, which reveals the quantitative relationship between the TVOC degradation rate and the photocatalytic process parameter.The results reveal that the TVOC release coefficient increases with increasing temperature and humidity and the three pretreatment methods can effectively remove TVOC in mats, in which washing and dryiny method works best, and the higher water temperature is beneficial to the release of TVOC.TiO2nanotubes arrays(TNAs) were prepared by anodic oxidation and were characterized by SEM, the results have showed that the nanotubes morphology is related to the solvent; ethylene glycol which is of moderate viscosity and conductivity is suitable to be solvent for preparation of TNAs; the anode area is too large or too small to generate nanotubes. Better morphology TNAs have been prepared with the ratio of anode area to electrolyte volume being0.05cm-1and the appropriate electrode gap.On the basic of mass transfer theory of TVOC molecular in nanotube, The TVOC photocatlytic degration rate model in TNAs has been proposed and model parameter has been estimated. And model values were compared with the experimental data, the error was less than20%. The model shows there is an optimal diameter for the maximum degradation rate.The preparation processes of Fe2O3/TNAs and Cu2O/TNAs composite nanotubes with better photocatalytic activity have been studied by experiment. The paper analyses the morphology, the optical response of Fe2O3/TNAs and Cu2O/TNAs and TVOC degradation effects on them, the results show the TVOC degradation effect on Cu2O/TNAs is better than on Fe2O3/TNAs, which are related to the Fe2O3and Cu2O amount, and the TVOC degradation on Fe2O3/TNAs and Cu2O/TNAs meets first-order kinetics.The effects of Cu content, temperature, humidity, oxygen content on photocatalytic degradation of TVOC were studied, and the kinetic model has been established. And model values were compared with the experimental data, the error was less than20%. The model shows the TVOC degradation effect is best when the doped-copper content, oxygen content and humidity is31.37%,36.92%and33.71%,respectively.

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