【作者】 吉钰纯；

【导师】 江学良；

【作者基本信息】 武汉工程大学 ， 材料物理与化学， 2011， 硕士

【摘要】 无机纳米空心球与实心球材料相比有较小的密度、较大的比表面积、中空结构、高的热稳定性能,并且具有特殊的电、光、磁等特性,并且空心球的壳层具有吸附、选择性渗透等特性,主要应用在化学储存、光子晶体、药物控制释放、催化载体以及作为填料等领域。到目前为止,人们已经通过不同的方法制备出很多不同的空心球材料,如:碳空心球、金属空心球、陶瓷空心球、无机纳米半导体空心球、金属氧化物空心球等等。但有关无机复合空心球和稀土纳米空心球研究较少。本论文以聚苯乙烯纳米微球为模板,不同的目标前躯体,利用溶胶-凝胶法和煅烧法分别制备出SiO₂、SiO₂/TiO₂、Y₂O₃和CeO₂空心球,并研究其功能化性能。利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、红外光谱分析（FTIR）、X射线衍射（XRD）等测试对所制备纳米空心球的结构进行表征,主要研究结果如下:1.利用两阶段种子乳液聚合法制备出单分散的丙烯酸共聚苯乙烯P（St-AA）微球,得到的微球具有单分散好、粒径分布可控、表面易于功能化等优点,第一阶段种子的粒径大小约为120nm左右,第二阶段粒径大小为250nm左右。2.以P（St-AA）微球作为模板,以正硅酸乙酯（TEOS）作为硅源,利用溶胶-凝胶法制备出P（St-AA）/SiO₂复合微球,于550oC下高温煅烧5h去除模板得到SiO₂空心球;将P（St-AA）/SiO₂复合微球作为模板,采用溶胶-凝胶法制备出P（St-AA）/SiO₂/TiO₂复合微球,再在550oC高温煅烧5h,制备出SiO₂/TiO₂复合空心球。对SiO₂/TiO₂复合空心球进行各种表征的结果表明,以P（St-AA）作为模板,溶胶凝胶法制备的SiO₂空心球和SiO₂/TiO₂空心球的球形度较好,微球表面比较光滑、粒径比较均一、SiO₂空心球粒径大小约为280nm,壳层厚度约为20nm,SiO₂/TiO₂空心球的粒径约为290nm,壳层厚度约为20nm,SiO₂/TiO₂空心球相对于SiO₂空心球的粒径略微稍有收缩。3.以六水硝酸钇作为钇源,采用三乙醇胺作为沉淀剂,浓氨水作为水解硝酸钇的物质,以（NH4）2SO4作为表面改性剂,于900℃下高温煅烧去除P（St-AA）微球模板,成功的制备出Y₂O₃空心球,其粒径约为100nm,壁厚约为20nm。Y₂O₃空心球与橡胶进行复合制备出聚合物-Y₂O₃复合材料,该材料具有良好的低频吸声性能。4.以P（St-AA）作为模板,六水硝酸铈作为铈源,采用尿素作为沉淀剂,以PVP作为表面改性剂,于600℃下高温煅烧去除P（St-AA）微球模板,成功的制备出CeO₂空心球, CeO₂空心球的晶型完好,其粒径约为250nm,壁厚约为10nm。将CeO₂空心球,进行废水模拟实验,发现CeO₂空心球对甲基蓝溶液具有良好的脱色性能。更多还原

【Abstract】 Compared with solid spheres, Inorganic nano hollow spheres has low density, large surface area, hollow structure, high thermal stability, so it can be applied to chemical storage, photonic crystals, drug controlled release systems, catalysis as well as the fillers and the other fields. So far, it has been prepared by many different methods of hollow spheres of different materials, such as: carbon hollow spheres, metal spheres, ceramic spheres, hollow spheres of inorganic semiconductor nanoparticles, metal oxide hollow spheres and so on. But less research on composite hollow spheres and nano rare earth hollow spheres.In this paper, SiO₂、SiO₂/TiO₂、Y₂O₃ and CeO₂ hollow spheres were prepared by using nano polystyrene spheres as the template, basic on different taget substrate, sol-gel and calcining method. The synthesized products were characterized by Scanning electron microscopy （SEM）, Transmission Electron Microscope （TEM）, Fourier infrared spectroscopic analysis （FTIR） and X-ray Diffraction （XRD） etc. The main study results as follows:1. Using two-stage seeded emulsion mathod to prepare monodisperse polystyrene P（St-AA） microspheres, the obtained P（St-AA） spheres with a good monodisperse, particle size distribution was controllable, surface easy to functional, etc. The first phase of the seed particle size was approxmate 120nm, the second phase particle size is about 250nm.2. Used the P（St-AA） microspheres as the templates, TEOS as silicon resource, use the sol-gel method to prepare P（St-AA）/SiO₂ composite microspheres, then they were calcined at 550℃for 5h to removal the P（St-AA） template to form SiO₂ hollow spheres; Used P（St-AA）/SiO₂ composite microspheres as the template by sol-gel method to prepare P（St-AA）/SiO₂/TiO₂ composite microspheres, and then calcined at 550℃for 5h, then we get the SiO₂/TiO₂ composite hollow spheres. The various characterization results of SiO₂/TiO₂ composite hollow spheres showed that using the P（St-AA） as the template, sol-gel method to prepare SiO₂ hollow spheres and SiO₂/TiO₂ hollow spheres had good sphericity, smooth surface, relatively homogeneous particle size, SiO₂ hollow sphere particle size was about 280nm, shell thickness was about 20nm, SiO₂/TiO₂ hollow microsphere particle size was about 290nm, shell thickness was about 20nm, SiO₂/TiO₂ hollow spheres relative to the size of SiO₂ hollow spheres shrink slightly.3. Used yttrium nitrate hexahydrate as the yttrium resource, triethanolamine as precipitating agent,concentrated ammonia as the material to hydrolysis nitricyttrium, and （NH4）2SO4 as a surface modification agent, then were calcined at 900℃to removal P（St-AA） microspheres and successfully prepared Y₂O₃ hollow spheres. The particles size was about 100nm, the wall thickness was about 20nm. Used the Y₂O₃ hollow spheres composited with rubber polymer to prepare the Y₂O₃ hollow sphere/ rubber polymer composite material, and the obtened material have a very good property of low frequency sound absorption.4. The P（St-AA） as template-agent, cerium nitrate hexahydrate as the cerium resource, urea as precipitating agent and PVP as surface modification agent to prepare P（St-AA）/CeO₂ composite spheres. Then they were calcined at 600℃to removal P（St-AA） spheres were successfully prepared the CeO₂ hollow spheres. The CeO₂ hollow spheres were perfect with crystals, theirs size was about 250nm, the wall thickness was about 10nm. We use the CeO₂ hollow spheres to degrade simulation dye effluents with methylene blue with a good bleaching performance.更多还原