过渡金属离子掺杂的介孔二氧化硅材料及几种MOFs材料光催化氧化四氢萘制备α-四氢萘酮的研究

发布时间：2018-12-07 12:23

【摘要】：α-四氢萘酮是一种十分重要的化工中间体。α-四氢萘酮现有的制备工艺常常存在着反应工艺复杂繁琐、原料昂贵、生产成本高、产率低下、产物分离提纯困难、污染严重、耗能高等一系列难以克服的严重问题,需要寻求解决的办法。光催化技术在降解有机污染物、治理重金属污染、解决能源问题等方面有很好的应用前景。光催化体系中需要研究的重点是高效的光催化剂。介孔材料在作为催化载体时,其内部的纳米级别孔道可以作为各种反应的微型反应器,大幅提升反应的效率。将介孔材料应用于光催化氧化四氢萘制备α-四氢萘酮的研究目前还未见报道。本文选取了介孔材料作为研究重点,首次将其应用于光催化氧化四氢萘制备α-四氢萘酮的体系中,考察了材料的光催化性能。论文的主要研究内容有：(1)制备了螺旋介孔二氧化硅纳米棒材料,并在该材料上掺杂了几种金属,还制备了HKUST-1、Fe-MIL-101、Ti-MIL-125与Cr-MIL-101这几种材料,通过X射线衍射、比表面测试、扫描电子显微镜、透射电子显微镜等手段对得到的材料进行了表征,研究了材料的各项性质；还制备了掺杂金属的MCM-41材料,将其用于对照试验实验。(2)将制备的材料应用于光催化氧化四氢萘制备α-四氢萘酮的体系中,使用气相色谱法考察了对金属掺杂量、催化剂用量、氧化剂用量、溶剂种类、光源类型等一系列因素对反应的影响,筛选了效果最好的材料并得出了相应的最佳的反应条件。实验表明,使用掺杂5%铜的螺旋介孔二氧化硅纳米棒材料时,最优反应条件为：四氢萘5 mL,双氧水5 mL,催化剂10 mg,无溶剂环境,800 W氙灯作为光源,室温反应8 h,反应结束后四氢萘的转化率为21.4%,α-四氢萘酮的选择性为62%,理论产率为13.3%；使用Ti-MIL-125材料时,最优反应条件为：四氢萘5 mL,双氧水8 mL,催化剂10 mg,无溶剂环境,800 W氙灯作为光源,室温反应8h,反应结束后α-四氢萘的转化率为15.6%,α-四氢萘酮的选择性为71%,理论产率为11.1%。在与其他材料的性能对比中,相同的反应体系下,本文中介绍材料的光催化性能均优于商业化Degussa P25材料与掺杂金属的MCM-41材料。
[Abstract]:伪 -tetrahydronaphthone is a very important intermediate in chemical industry. The existing preparation process of 伪 -tetrahydronaphthone often has complex reaction process, expensive raw material, high production cost, low yield, difficult separation and purification of the product, and serious pollution. A series of insurmountable serious problems, such as high energy consumption, need to be solved. Photocatalytic technology has a good application prospect in degradation of organic pollutants, treatment of heavy metal pollution, energy problems and so on. The focus of research in photocatalytic system is high efficient photocatalyst. When mesoporous materials are used as catalytic carriers, the internal nano-pore channels can be used as microreactors for various reactions, and the efficiency of the reactions can be greatly improved. The application of mesoporous materials in photocatalytic oxidation of tetranaphthalene to 伪 -tetrahydronaphthalone has not been reported. In this paper, mesoporous materials were selected as the focus of the study. The mesoporous materials were used for the first time in the system of photocatalytic oxidation of tetranaphthalene to prepare 伪 -tetrahydronaphthalene, and the photocatalytic properties of the materials were investigated. The main contents of this thesis are as follows: (1) the helical mesoporous silica nanorods were prepared, and several metals were doped into the materials, and HKUST-1,Fe-MIL-101,Ti-MIL-125 and Cr-MIL-101 materials were also prepared. The obtained materials were characterized by X-ray diffraction, specific surface measurement, scanning electron microscope and transmission electron microscope, and the properties of the materials were studied. The MCM-41 materials doped with metal were also prepared and used in the controlled experiment. (2) the prepared materials were used in the system of photocatalytic oxidation of tetralin to prepare 伪 -tetralin, and the doping amount of p-metal was investigated by gas chromatography. A series of factors, such as the amount of catalyst, the amount of oxidant, the type of solvent, the type of light source, etc., have influenced the reaction. The best materials have been selected and the optimum reaction conditions have been obtained. The experimental results show that the optimum reaction conditions are as follows: Tetrahydronaphthalene 5 mL, hydrogen peroxide 5 mL, catalyst 10 mg, solvent free environment, 800W xenon lamp as light source, room temperature reaction 8 h, when 5% copper doped helical mesoporous silica nanorods are used, the reaction conditions are as follows: Tetrahydronaphthalene 5 mL, hydrogen peroxide 5 mL, catalyst 10 mg, solvent free environment. After the reaction, the conversion of tetralin was 21.4g, the selectivity of 伪 -tetrahydronaphthalone was 62 and the theoretical yield was 13.3; When using Ti-MIL-125 material, the optimum reaction conditions are as follows: Tetrahydronaphthalene 5 mL, hydrogen peroxide 8 mL, catalyst 10 mg, solvent free environment, 800W xenon lamp as light source, room temperature reaction 8 h, After the reaction, the conversion of 伪 -tetrahydronaphthalene was 15.6g, the selectivity of 伪 -tetrahydronaphthalene was 71 and the theoretical yield was 11.1. In comparison with other materials, in the same reaction system, the photocatalytic properties of the materials described in this paper are superior to those of commercial Degussa P25 and metal-doped MCM-41.
【学位授予单位】：云南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.36

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