微纳米无机功能材料的形貌控制及其表面MOFs化

发布时间：2018-02-04 07:09

本文关键词： 微纳米无机功能材料形貌控制表面MOFs化　出处：《北京科技大学》2015年博士论文　论文类型：学位论文

【摘要】：微纳米无机功能材料由于具有独特的磁、光、电、催化等性能,受到了全世界科研工作者的广泛关注。材料的形貌、结构、尺寸对其性能有着重要影响,因此探索无机功能材料的可控合成方法对于提升其性能具有重要意义。本论文从无机功能材料的控制合成入手,基于络合沉淀法制备了一系列具有特殊形貌、新颖结构的无机功能材料,提出了其可能的生长机制并发展了新的可控合成方法,探索了其在催化领域的应用并研究了材料微纳米结构与性能之间的构效关系,为微纳米无机功能材料的结构设计、性能调控及其在相关领域的实际应用提供了理论和实验依据。基于络合沉淀法,发展了一种制备多级结构微纳米无机功能材料的普适性方法,利用添加剂的络合作用和结构导向作用控制反应速度及产物的形成过程,制备得到了多种具有新颖结构的无机功能材料(双轮状组装体结构镍钴氢氧化物/氧化物,两面刷结构掺镍氢氧化钴/四氧化三钴及yolk/shell碱式硫酸铜),并通过控制实验参数实现了产物形貌和尺寸的调控。在制备多种结构无机功能材料的基础上,系统研究了添加剂加入量、反应温度、pH环境、前躯体种类、前躯体与络合剂浓度比等因素对产物形貌的影响,提出了上述微纳米多级结构产物的生长机制,为微纳米材料的可控合成提供了理论基础。利用自模板法实现了特定无机功能材料的表面原位转化,制备得到了无机功能材料@MOFs,实现了MOFs优异的结构特性(超大的比表面积,均匀的孔径分布,可控的拓扑结构及可调的孔径)和微纳米粒子催化特性的优势集成,克服了传统的层层自组装法制备微纳米粒子@MOFs存在的反应条件苛刻、周期长且后处理复杂等缺点。围绕所制备的多级结构微纳米无机功能材料,探索了其在催化领域的应用研究,上述产物对烯烃环氧化反应、缩醛反应和醇的分子氧氧化反应等反应具有优异的催化效果。
[Abstract]:Due to their unique magnetic, optical, electrical and catalytic properties, micro-nano inorganic functional materials have been widely concerned by researchers all over the world. The morphology, structure and size of the materials have an important impact on their properties. Therefore, it is very important to explore the controllable synthesis method of inorganic functional materials for improving their properties. In this paper, a series of special morphologies were prepared based on complex precipitation method, starting with the controlled synthesis of inorganic functional materials. The possible growth mechanism of inorganic functional materials with novel structure was proposed and a new controllable synthesis method was developed. Their applications in the field of catalysis were explored and the structure-activity relationship between microstructures and properties of the materials was studied. It provides theoretical and experimental basis for the structure design, performance control and practical application in the related fields of micro and nano inorganic functional materials. Based on the complexation precipitation method, a universal method for the preparation of multilevel structure microinorganic functional materials was developed. The reaction rate and the formation process of the product were controlled by the complexation and structure-oriented action of additives. A variety of inorganic functional materials (nickel cobalt hydroxide / oxide) with novel structure were prepared. The structure of two-sided brush was doped with nickel hydroxide cobalt oxide / cobalt trioxide and yolk/shell basic copper sulfate. The morphology and size of the product were controlled by controlling the experimental parameters. On the basis of the preparation of various inorganic functional materials, the effects of additives, reaction temperature and pH environment, the species of precursor and the concentration ratio of precursor to complexing agent on the morphology of the product were studied systematically. The growth mechanism of the products is proposed, which provides a theoretical basis for the controllable synthesis of micro- and nanocrystalline materials. Self-template method was used to realize the surface in-situ conversion of specific inorganic functional materials, and the inorganic functional material @ @ @ MOFs was prepared, which realized the excellent structural properties of MOFs (large specific surface area). Uniform pore size distribution, controllable topology and adjustable pore size) are integrated with the catalytic properties of microparticles. It overcomes the disadvantages of the traditional layer-by-layer self-assembly method in preparing micro-and nano-particles, such as harsh reaction conditions, long period and complex post-processing. Based on the multilevel structure microinorganic functional materials, the application of these materials in the field of catalysis was explored, and the epoxidation of olefin by the above products was studied. The acetal reaction and the molecular oxygen oxidation of alcohol have excellent catalytic effect.
【学位授予单位】：北京科技大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383

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