聚合物基底诱导贵金属自组装微纳米超结构形貌调控及机理研究

发布时间：2018-03-09 02:11

本文选题：贵金属纳米粒子　切入点：聚合物刷　出处：《宁波大学》2015年硕士论文　论文类型：学位论文

【摘要】：作为目前科学领域最热门的方向之一,贵金属微纳米结构研究所取得的成果显示其在合成化学、材料科学、物理、生物、医学等众多科技领域有着巨大的发展潜力和广泛的应用前景。将小分子或者粒子组装成特定的结构是形成新材料的一个重要过程。由于纳米粒子间激子、磁偶极矩、表面等离子体共振等相互作用,赋予组装成的超结构新的电磁学、光学、催化等性能。目前已经有多种方法可以实现贵金属纳米粒子到微纳米超结构的转变,其中利用有机物辅助实现金属纳米粒子的组装,形成特定结构的有机无机超结构复合材料一直是新材料研究领域中最具活力,也是实现纳米材料应用的一个重要途径。因此有机材料与无机材料的结合对未来科技,经济和社会发展有着重要的影响。有机材料中,高分子聚合物拥有小分子物质所不具有的独特性质,成了制备金属微纳米结构基质或者基底的优先选择。本文分别选择聚合物刷,聚合物薄膜和聚合物胶体粒子作为基底制备贵金属/聚合物微纳米结构,并对结构、组成与应用进行表征探索。具体研究内容如下:以聚合物刷为基底制备银微纳米结构及SERS方面的应用。首先利用紫外光引发聚合在硅片表面制备一层聚苯乙烯刷,通过磺化在苯环上引入-SO3H基团。以磺化聚苯乙烯刷为基底吸附银前躯体,然后一步还原制备银微纳米超结构,并且通过改变前躯体吸附时间调控微纳米结构的形状。以制备的聚合物刷基底/银微纳米超结构作为SERS基底,研究了在SERS方面的应用。实验结果现实增强效果很好,当探针分子浓度低于10-12 mol/l时,依然可以观测到明显的探针分子特征峰。聚合物膜为基底制备贵金属微纳米结构并用金属置换法制备双金属微纳米结构。通过烷基化反应,在硅片表面接枝不同厚度的APTES膜和采用层层自组装法成功的制备出了PAA和PEI聚合物膜。由于聚物膜不同的物理化学性质,在聚合物膜表面制备出不同形状的银微纳米超结构。并通过金属腐蚀置换法探索了这种三维多孔网络状的结构在制备双金属微纳米超结构方面的应用。以聚合物胶体粒子为模板制备聚合物胶体粒子/银纳米结构。通过简单的无皂乳液聚合制备出聚苯乙烯-聚甲基丙烯酸的共聚胶体粒子。改变单体的配比,胶体粒子呈现出不同的结构形态。利用甲基丙烯酸的电负性,不需要对胶体粒子改性或者修饰,就可以通过静电吸附还原的方法制备出带有银壳的聚合物贵金属微纳米复合结构。
[Abstract]:As one of the most popular fields in science, the achievements of noble metal microstructures research show that they are used in synthetic chemistry, material science, physics, biology, Medicine and many other fields of science and technology have great potential for development and wide application prospects. Assembling small molecules or particles into specific structures is an important process in the formation of new materials. Surface plasmon resonance (SPR) and other interactions endow the assembled superstructures with new electromagnetic, optical, catalytic and other properties. Among them, organically assisted metal nanoparticles are assembled, and organic-inorganic superstructure composites with specific structures are always the most active materials in the field of new materials. It is also an important way to realize the application of nanomaterials. Therefore, the combination of organic and inorganic materials will have an important impact on the development of science and technology, economy and society in the future. Polymeric polymers have unique properties that small molecules do not have, making them the preferred choice for the preparation of metal microstructures or substrates. In this paper, polymer brushes are selected, respectively. Polymer thin films and polymer colloidal particles were used as substrates to prepare noble metal / polymer microstructures, The main contents are as follows: preparation of silver microstructures based on polymer brushes and application of SERS. Firstly, a layer of polystyrene brushes was prepared on the surface of silicon wafers by ultraviolet photoinitiation polymerization. The silver precursor was adsorbed on the sulfonated polystyrene brush by the introduction of -SO _ 3H group on the benzene ring by sulfonation, and then the silver micro-nanometer superstructure was prepared by one step reduction. The shape of microstructures was regulated by changing the adsorption time of precursor body. The polymer brush / silver microsuperstructures were used as SERS substrates to study the application of SERS. The experimental results showed that the enhancement effect was very good. When the molecular concentration of the probe was lower than 10-12 mol/l, the characteristic peak of the probe could still be observed. The polymer membrane was used as the substrate to prepare the noble metal microstructures and the bimetal microstructures were prepared by the method of metal replacement. PAA and PEI polymer films were successfully prepared by grafted APTES films with different thickness on the surface of silicon wafers and by layer-by-layer self-assembly method. Due to the different physical and chemical properties of the polymer films, Silver microstructures with different shapes were prepared on the surface of polymer films. The application of this three-dimensional porous network structure to the preparation of bimetallic microstructures was explored by metal corrosion replacement. Polymer colloid particles / silver nanostructures were prepared by using colloidal particles as templates. Polystyrene-polymethacrylic acid copolymer colloid particles were prepared by simple soap-free emulsion polymerization. Colloidal particles take on different structural forms. Using the electronegativity of methacrylic acid, there is no need to modify or modify colloidal particles. The polymer noble metal microcomposite structure with silver shell can be prepared by electrostatic adsorption and reduction.
【学位授予单位】：宁波大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1

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