有机功能化介孔材料吸附抗生素污染物研究

发布时间：2018-05-20 04:17

本文选题：有机功能化介孔材料 + click反应　；参考：《大连理工大学》2015年硕士论文

【摘要】：有机基团修饰的介孔氧化硅材料在许多领域表现出潜在的应用价值,包括催化、吸附、药物传递、环境保护等。由于具有高的比表面积、大而可调的孔径、多样的孔结构,功能化介孔材料是一种很好的去除水体中污染物的吸附剂。通过有机基团的引入,可以强化介孔材料与吸附质之间的作用力,例如静电作用、亲/疏水性、π-π键以及络合作用等,从而增强介孔材料的吸附性能。抗生素类药物进入水环境后,通过传统水处理技术难以去除,是一种新兴的环境污染物。围绕有机功能化的介孔材料合成及吸附去除抗生素污染物的问题,本论文开展了以下研究：共缩聚法合成的叠氮基功能化的介孔SBA-15材料(N3-SBA-15)作为反应的原料,通过click反应将有机基团引入到介孔材料中,结果表明反应高效、产率高。同时用传统的共缩聚法和后嫁接法合成SBA-15类功能化材料,三种合成方法得到的材料具有相似的官能团。所有材料用于抗生素吸附实验,结果显示相似的官能团具有相似的吸附趋势。但通过click反应制备有机基团功能化介孔材料更加方便、快速并且对材料结构影响较小。由此证明click反应修饰介孔材料的新应用：可以用来迅速筛选吸附抗生素功能基团。上述研究表明介孔材料中引入有机基团,增加材料的疏水性可以提高材料对抗生素的吸附性能。提高材料的疏水性除了可以在材料表面引入有机基团,还可以在材料的表面和骨架中同时引入有机基团。因此,我们进一步合成了骨架中含有乙烷功能团,表面可以通过click反应修饰不同功能团的叠氮基功能化的周期性介孔有机硅材料(PMOs).实验显示click反应同样快速、高产率。此外,修饰后的PMOs比单纯叠氮功能化PMOs对抗生素(盐酸环丙沙星)的吸附容量明显提高(241μg/g)。研究表明,click反应可以在PMOs材料中引入多种官能团,环境应用潜力巨大。为了研究吸附剂与吸附质之间的作用力对吸附效果的影响,又做了如下实验。用共缩聚法合成SBA-15和SH-SBA-15、进而合成SO3H-SBA-15。三种材料做氟喹诺酮类抗生素吸附实验,结果证明SO3H-SBA-15有突出的吸附性能。通常我们认为吸附剂的疏水性对吸附的影响会强于它们与吸附质之间的静电作用力的影响。但是经过实验以及材料结构分析,对这一现象的推断是,SO3H-SBA-15与抗生素分子间存在的静电吸引作用比亲／疏水作用更有利于吸附的进行。此外,SO3H-SBA-15在重复利用三次后吸附性能仍然没有明显降低,可以说是一种非常有潜力的吸附剂。
[Abstract]:Organic group modified mesoporous silica materials have shown potential applications in many fields, including catalysis, adsorption, drug delivery, environmental protection and so on. Because of its high specific surface area, large and adjustable pore size and diverse pore structure, functionalized mesoporous material is a good adsorbent for removing pollutants in water. The interaction between mesoporous materials and adsorbents, such as electrostatic interaction, hydrophobicity, 蟺-蟺 bond and complexation, can be strengthened by the introduction of organic groups, thus enhancing the adsorption properties of mesoporous materials. After antibiotics enter the water environment, it is difficult to remove by traditional water treatment technology, so it is a new environmental pollutant. In this paper, the synthesis of organic functionalized mesoporous materials and the removal of antibiotic pollutants by adsorption have been studied as follows: the azido-functionalized mesoporous SBA-15 materials (N3-SBA-15) synthesized by co-condensation were used as raw materials for the reaction. The organic groups were introduced into mesoporous materials by click reaction. The results showed that the reaction was efficient and the yield was high. At the same time, the SBA-15 functional materials were synthesized by the traditional co-condensation and post-grafting methods. The materials obtained by the three methods have similar functional groups. All the materials were used in antibiotic adsorption experiments. The results showed that the similar functional groups had similar adsorption trend. However, the preparation of organic group functionalized mesoporous materials by click reaction is more convenient, rapid and has little effect on the structure of the materials. The new application of click reaction modified mesoporous materials can be used to quickly screen functional groups of adsorbed antibiotics. The results show that the addition of organic groups and the increase of hydrophobicity of mesoporous materials can improve the adsorption properties of antibiotics. To improve the hydrophobicity of the material, not only organic groups can be introduced on the surface of the material, but also organic groups can be introduced into the surface and skeleton of the material at the same time. Therefore, we further synthesized the ethane functional group in the skeleton. The surface can be modified by click reaction. The periodic mesoporous organosilicon materials with different functional groups can be modified by click reaction. The experiment showed that click reaction was also fast and high yield. In addition, the adsorption capacity of modified PMOs for antibiotics (ciprofloxacin hydrochloride) was significantly higher than that of azido-functionalized PMOs. The results show that the click reaction can introduce a variety of functional groups into PMOs materials and has great potential for environmental application. In order to study the effect of the force between adsorbent and adsorbate on the adsorption effect, the following experiments have been done. SBA-15 and SH-SBA-15 were synthesized by co-condensation, and then SO3H-SBA-15 was synthesized. The adsorption experiments of fluoroquinolones by three kinds of materials show that SO3H-SBA-15 has outstanding adsorption properties. It is generally considered that the hydrophobicity of adsorbents has a stronger effect on the adsorption than the electrostatic force between them and the adsorbates. However, it is inferred that the electrostatic attraction between SO3H-SBA-15 and antibiotic molecules is more favorable to the adsorption than the hydrophilic / hydrophobic interaction. In addition, the adsorption properties of SO3H-SBA-15 were not significantly decreased after three times of reuse, which can be said to be a very potential adsorbent.
【学位授予单位】：大连理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X52;O647.3

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