无机/有机“核/壳”复合结构及空壳材料的制备与表征
摘要
近年来，核壳复合结构及空壳结构材料由于具有特异物理、化学性质，引起了科学界的浓厚兴趣。
本文在大量文献调研的基础上，对核壳结构及空壳结构材料的合成方法进行了研究，并取得了如下成果：
(1)发展了一种新的基于表面吸附，原位氧化的具有核壳式结构的单分散性的二氧化硅／聚吡咯(Ppy)复合微球的制备方法。并对制备好的SiO_2／Ppy复合微球进行化学腐蚀处理，制备出壁厚可裁剪的空腔导电高分子球。SiO_2／Ppy复合微球具有核壳式结构，Ppy纳米颗粒在SiO_2中心形成均匀的壳层(40 nm～70 nm)。空腔导电高分子球的空腔基本保留着原模版的球形，内外壁轮廓清晰。制备出的SiO_2／PPy复合微球及空腔高分子球在材料化学及生物医药技术领域均有着广泛的应用前景。考察了温度、单体的加入量对复合微球形貌的影响；对制备得到的复合微球进行化学腐蚀，可得到聚吡咯空腔微球，试验结果显示，在适合的反应温度下，随着单体加入量的增加，空腔微球的壁厚增加。
(2)利用上述研究的机理对磁性Fe_3O_4粒子进行聚吡咯的包覆，形成磁性聚吡咯导电材料，通过分析各种表征手段的结果，解释了聚吡咯与Fe_3O_4粒子之间可能存在的相互作用。对Fe_3O_4粒子和复合粒子的磁性能及吸波性能进行检测，复合粒子在吸波性能上表现出比单一Fe_3O_4粒子更为优良的性能。
(3)利用葡萄糖的水热缩合反应制备胶体碳球，并以碳球为核层材料，在水溶液中吸附金属离子，形成C／M~(x+)的复合结构，在进行煅烧处理后，形成了金属氧化物空心材料，研究参杂Eu~(3+)离子的Co空心球的荧光性能。并对碳球和金属空球的形成机理进行了讨论。
This work studies about controllable fabrication of SiO_2 andSiO_2/polypyrrole core/shell particles. An improved ethanol hydrolyzationprogress has been used in the synthesis of SiO_2 particles; then an in-situpolymerization route has been developed to synthesize SiO_2/polypyrrolecore/shell particles with controllable shell thickness. Hollow polypyrrolespheres could be obtained via etched method by HF. The influences oftemperature and addition volume of pyrrole monomer on the shapes ofproduct are explored. The morphology, structure and chemicalcomposition of the SiO_2、core/shell particles and hollow spheres areobtained in this study are investigated by SEM, TEM, and FTIR spectrum.The results of TEM and SEM show that PPy has formed a uniform shellround the core. The diameter of hollow sphere is about 400 nm. Thethickness of shell could be adjusted in 40 nm～70 nm by changing thepyrrole monomer's concentration.
Using the same fabrication mechanism, we have fabricatedFe_3O_4/PPy core/shell particles. The result of FTIR、magenetic andelectromagnetism implies there is an interaction between Fe_3O_4 and PPy.Fe_3O_4/PPy core/shell particles have a wider microwave absorption bandthan that of Fe_3O_4.
A method for the synthesis of metal oxide hollow spheres has beendeveloped by using carbonaceous polysaccharide microspheres preparedfrom saccharide solution as templates. Hollow spheres of a series of metaloxides have been prepared in this way. The method involves the initialabsorption of metal ions from solution into the functional surface layer ofcarbonaceous saccharide microspheres; these are then densified andcross-linked in a subsequent calcination and oxidation procedure to formmetal oxide hollow spheres. TEM has been used to characterize thestructures. The result of the fluorescence spectrum of La_2O_3: Eu hollowspheres show the hollow structure can influence the fluorescenceperformance of La_2O_3: Eu hollow spheres.
本文在大量文献调研的基础上，对核壳结构及空壳结构材料的合成方法进行了研究，并取得了如下成果：
(1)发展了一种新的基于表面吸附，原位氧化的具有核壳式结构的单分散性的二氧化硅／聚吡咯(Ppy)复合微球的制备方法。并对制备好的SiO_2／Ppy复合微球进行化学腐蚀处理，制备出壁厚可裁剪的空腔导电高分子球。SiO_2／Ppy复合微球具有核壳式结构，Ppy纳米颗粒在SiO_2中心形成均匀的壳层(40 nm～70 nm)。空腔导电高分子球的空腔基本保留着原模版的球形，内外壁轮廓清晰。制备出的SiO_2／PPy复合微球及空腔高分子球在材料化学及生物医药技术领域均有着广泛的应用前景。考察了温度、单体的加入量对复合微球形貌的影响；对制备得到的复合微球进行化学腐蚀，可得到聚吡咯空腔微球，试验结果显示，在适合的反应温度下，随着单体加入量的增加，空腔微球的壁厚增加。
(2)利用上述研究的机理对磁性Fe_3O_4粒子进行聚吡咯的包覆，形成磁性聚吡咯导电材料，通过分析各种表征手段的结果，解释了聚吡咯与Fe_3O_4粒子之间可能存在的相互作用。对Fe_3O_4粒子和复合粒子的磁性能及吸波性能进行检测，复合粒子在吸波性能上表现出比单一Fe_3O_4粒子更为优良的性能。
(3)利用葡萄糖的水热缩合反应制备胶体碳球，并以碳球为核层材料，在水溶液中吸附金属离子，形成C／M~(x+)的复合结构，在进行煅烧处理后，形成了金属氧化物空心材料，研究参杂Eu~(3+)离子的Co空心球的荧光性能。并对碳球和金属空球的形成机理进行了讨论。
This work studies about controllable fabrication of SiO_2 andSiO_2/polypyrrole core/shell particles. An improved ethanol hydrolyzationprogress has been used in the synthesis of SiO_2 particles; then an in-situpolymerization route has been developed to synthesize SiO_2/polypyrrolecore/shell particles with controllable shell thickness. Hollow polypyrrolespheres could be obtained via etched method by HF. The influences oftemperature and addition volume of pyrrole monomer on the shapes ofproduct are explored. The morphology, structure and chemicalcomposition of the SiO_2、core/shell particles and hollow spheres areobtained in this study are investigated by SEM, TEM, and FTIR spectrum.The results of TEM and SEM show that PPy has formed a uniform shellround the core. The diameter of hollow sphere is about 400 nm. Thethickness of shell could be adjusted in 40 nm～70 nm by changing thepyrrole monomer's concentration.
Using the same fabrication mechanism, we have fabricatedFe_3O_4/PPy core/shell particles. The result of FTIR、magenetic andelectromagnetism implies there is an interaction between Fe_3O_4 and PPy.Fe_3O_4/PPy core/shell particles have a wider microwave absorption bandthan that of Fe_3O_4.
A method for the synthesis of metal oxide hollow spheres has beendeveloped by using carbonaceous polysaccharide microspheres preparedfrom saccharide solution as templates. Hollow spheres of a series of metaloxides have been prepared in this way. The method involves the initialabsorption of metal ions from solution into the functional surface layer ofcarbonaceous saccharide microspheres; these are then densified andcross-linked in a subsequent calcination and oxidation procedure to formmetal oxide hollow spheres. TEM has been used to characterize thestructures. The result of the fluorescence spectrum of La_2O_3: Eu hollowspheres show the hollow structure can influence the fluorescenceperformance of La_2O_3: Eu hollow spheres.
引文
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