模板法合成核壳功能材料

模板法制备核壳功能材料是材料科学研究领域的一大热点引起了广泛的关注.本文结合本课题组在有机-无机核壳复合纳米粒子(空心球)领域的研究,较系统地评述了目前国内外利用模板法制备核壳粒子的研究进展,并概述了核壳纳米粒子(空心球)的发展前景和应用领域.     

纳米金掺杂中空微胶囊的制备与表征

将表面含有双键的二氧化硅微粒分散在纳米金和聚乙烯吡咯烷酮溶液中.在此溶液中以聚乙烯吡咯烷酮为模板聚合物进行丙烯酸的模板聚合,得到二氧化硅为核、聚丙烯酸/聚乙烯吡咯烷酮/纳米金为壳层的核壳结构微粒.用氢氟酸将二氧化硅微粒去除后,得到了纳米金粒子掺杂的微胶囊.分别用扫描电子显微镜和激光共聚焦显微镜表征了微胶囊在干态和湿态下的形貌.通过电子衍射和透射电子显微镜确证了纳米金粒子在微囊壁上的存在和分布.     

SiO2 /Au核壳结构纳米粒子的制备及表征

通过以金纳米粒子为表面晶种和壳生长的方法制备了金纳米壳包覆二氧化硅的复合纳米粒子。采用TEM 和UV-Vis对复合粒子进行了表征和研究，结果表明所得到的复合粒子粒径均匀、金纳米壳光滑完整，且壳厚度可通过反应物的用量来控制。当核半径与壳厚度之比在4到13之间变化时,复合粒子的光学共振峰在可见光区到近红外光区范围内可发生大于500 nm波长的移动。     

Au@SiO2核壳纳米粒子的制备及其表面增强拉曼光谱

采用柠檬酸钠还原氯金酸法制备金溶胶, 以正硅酸乙酯(TEOS)为硅源, 氨水作催化剂, 制备以金为核, 二氧化硅为壳的核壳纳米粒子. 金纳米粒子的粒径可以通过柠檬酸钠和氯金酸的比例控制, 通过调节TEOS的量和反应的时间可以控制二氧化硅壳层的厚度. 以苯硫酚为探针分子研究了核壳结构纳米粒子的表面增强拉曼散射(SERS)效应与二氧化硅壳层厚度之间的关系. 研究结果表明, 金内核电磁场增强效应随着二氧化硅壳层厚度的增加逐渐减弱, 且其衰减速度比具有相同尺度的双金属核壳结构纳米粒子的慢. 此外, 探针分子主要以物理作用吸附在二氧化硅的表面, 可通过洗涤方法将探针分子除去, 从而可使该复合结构基底用于循环SERS分析.     

以手性两亲小分子为模板剂制备介孔二氧化硅纳米空心球

以L-亮氨酸为手性源合成了手性阳离子两亲性小分子化合物L-18Leu6NEtBr,用其自组装体作为模板,氢氧化钠为催化剂,经溶胶-凝胶过程制备出介孔二氧化硅纳米空心球;分析了介孔二氧化硅纳米空心球的尺寸和孔径.结果表明,所制备的二氧化硅空心球直径约100nm;其介孔孔道平行于壳表面,孔径为3.1nm.     

磁性二氧化硅复合纳米粒子的合成及其与青铜器的相互作用研究

采用反相微乳液法, 合成了以PVP分散的磁性Fe₃O₄纳米粒子为核、SiO₂为壳并复合有荧光标记物钌联吡啶的核壳型复合功能纳米粒子. 在对该功能型二氧化硅复合纳米粒子进行TEM、荧光特性和磁性等特性表征的基础上, 重点研究了水溶性高聚物PVP溶液对Fe₃O₄纳米粒子的分散性, 并将其均匀的包入SiO₂壳中, 基于此研究了该功能型二氧化硅复合纳米粒子与青铜器之间的相互作用、以功能型复合纳米粒子为材料对青铜器腐蚀机理进行了在线、无损、实时监测以及将复合纳米材料从被分析体系中无损去除的方法, 发展了适合于去除吸附于青铜器文物表面的功能型纳米粒子的新方法. 这一研究结果为以该纳米粒子为基质构建适合于青铜器表面成分分析的纳米传感器奠定了基础.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

CeO2@Au核壳结构纳米粒子的合成与性质研究

采用沉淀法制备了球形CeO2纳米粒子,将其作为核粒子溶液,然后向其中滴加四氯合金酸溶液,在CeO2胶体表面利用柠檬酸钠还原[AuCl4]-离子,得到了CeO2@Au核壳结构纳米粒子。TEM分析表明,CeO2纳米粒子分散效果好,粒径为5 nm;CeO2@Au核壳粒子为球形,无团聚,平均粒径为15 nm。XRD分析表明,CeO2@Au核壳粒子为晶型结构,属于立方晶系,CeO2空间群为O5H-FM3M,Au的空间群为Fm-3m。UV-vis分析发现,CeO2@Au核壳粒子在300和520 nm处呈现出两个比较强的吸收峰,分别对应于CeO2胶体溶液的吸收峰和金粒子的表面等离子共振吸收峰。EDS分析了核壳结构CeO2@Au纳米粒子中存在Ce,O和Au 3种元素。XPS分析表明,Ce3d3/2和Au4f电子结合能与标准结合能相比发生了变化,说明CeO2与Au之间存在着相互作用。     

A novel and facile preparation method of hollow silica spheres containing small SiO2 cores

This article presents a novel and facile preparation method of hollow silica spheres with loading small silica inside. In this approach, positively charged SiO₂/polystyrene core‐shell composite particles were synthesized first, when the silica shells from the sol‐gel process of tetraethoxysilane were then coated on the surfaces of composite particles via electrostatic interaction, the polystyrene was dissolved subsequently even synchronously in the same medium to form hollow silica spheres with small silica cores. TEM, SEM, and FTIR measurements were used to characterize these composite spheres. Based on this study, some inorganic or organic compounds could be loaded into these hollow silica spheres. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3431–3439, 2007     

Fabrication of nanocapsules with Au particles trapped inside carbon and silica nanoporous shells

Carbon capsules with hollow cores and mesoporous shells (HCMS) containing entrapped Au particles were prepared by template replication from solid core/mesoporous shell silica spheres with encapsulated Au particles. The resulting HCMS carbon capsules were then nanocast one step further to generate Au-trapping hollow core silica capsules with nanostructured shells.     

Preparation of single-hole hollow polymer nanospheres by raspberry-like template method

Single-hole hollow polymer nanospheres were fabricated by raspberry-like template method using "graft-from" strategy through atom transfer radical polymerization (ATRP). Nanometer-sized silica spheres were covalently attached onto the surfaces of micrometer-sized silica spheres. Crosslinked polymer shells on the nano-sized spheres outside the attached area were formed by "graft-from" strategy through ATRP. After removal of the silica cores, single-hole hollow crosslinked polymer nanospheres were obtained. In this strategy, most of ATRP monomers may be used and thus many functional groups can be easily incorporated into the single-hole hollow crosslinked polymer nanospheres.     

Preparation of hollow titania and strontium titanate spheres using sol–gel derived silica gel particles as templates

A facile approach, based on polyelectrolyte-mediated electrostatic adsorption of a water-soluble titanium complex on colloidal templates and hydrothermal treatment, is presented for the formation of hollow titania (TiO₂) and strontium titanate (SrTiO₃) spheres. Monodispersed silica gel particles were prepared by the sol?Cgel method and adopted as core templates. Deposition of a water-soluble titanium complex, titanium (IV) bis(ammoniumlactato)dihydroxide (TALH), on the silica gel particles was carried out via the layer-by-layer assembly technique. Hollow spheres were successfully formed from the core?Cshell particles. The silica gel particles used as core templates dissolved during hydrothermal treatment because of the particles?? undeveloped siloxane network. In addition, the hydrothermal treatment induced crystallization of the hollow shells. Therefore, the hydrothermal treatment played two roles; removal of the silica templates and crystallization of the hollow shells. When deionized water was used, hollow TiO₂ spheres were obtained. Hollow SrTiO₃ spheres could also be formed when an aqueous solution of Sr(OH)₂ was used. The approach presented here could be exploited as a novel and sustainable approach for the fabrication of a range of different inorganic hollow spheres.     

Synthesis and utilization of monodisperse hollow polymeric particles in photonic crystals

We developed a process to fabricate 150-700 nm monodisperse polymer particles with 100-500 nm hollow cores. These hollow particles were fabricated via dispersion polymerization to synthesize a polymer shell around monodisperse SiO(2) particles. The SiO(2) cores were then removed by HF etching to produce monodisperse hollow polymeric particle shells. The hollow core size and the polymer shell thickness, can be easily varied over significant size ranges. These hollow polymeric particles are sufficiently monodisperse that upon centrifugation from ethanol they form well-ordered close-packed colloidal crystals that diffract light. After the surfaces are functionalized with sulfonates, these particles self-assemble into crystalline colloidal arrays in deionized water. This synthetic method can also be used to create monodisperse particles with complex and unusual morphologies. For example, we synthesized hollow particles containing two concentric-independent, spherical polymer shells, and hollow silica particles which contain a central spherical silica core. In addition, these hollow spheres can be used as template microreactors. For example, we were able to fabricate monodisperse polymer spheres containing high concentrations of magnetic nanospheres formed by direct precipitation within the hollow cores.     

A novel method for the fabrication of monodisperse hollow silica spheres

In this paper, we report a novel method for the fabrication of small monodisperse hollow silica spheres. In this approach, when silica shells were coated on polystyrene particles by the sol-gel method, the polystyrene cores were dissolved subsequently, even synchronously, in the same medium to form monodisperse hollow spheres. Neither additional dissolution nor a calcination process was needed to remove the polystyrene cores. Transmission electron microscopy, scanning electron microscopy, and porosity measurements were used to characterize the monodisperse hollow silica spheres.     

Ni hollow spheres as catalysts for methanol and ethanol electrooxidation

In this paper, we successfully synthesized Ni hollow spheres consisting of needle-like nickel particles by using silica spheres as template with gold nanoparticles seeding method. The Ni hollow spheres are applied to methanol and ethanol electrooxidation in alkaline media. The results show that the Ni hollow spheres give a very high activity for alcohol electrooxidation at a very low nickel loading of 0.10 mg cm⁻². The current on Ni hollow spheres is much higher than that on Ni particles. The onset potential and peak potential on Ni hollow spheres are more negative than that on Ni particles for methanol and ethanol electrooxidation. The Ni hollow spheres may be of great potential in alcohol sensor and direct alcohol fuel cells.     

A facile method for the preparation of monodisperse hollow silica spheres with controlled shell thickness

This article presents a facile, effective, mild synthesis process for well‐defined hollow spheres by using cationic polystyrene (PS) submicro‐particles as templates. In this approach, the cationic PS templates can be first prepared via emulsifier‐free polymerization by using the cationic monomer 2‐(methacryloyloxy) ethyltrimethylammonium chloride as comonomer, then, the silica shells from the sol‐gel process of tetraethoxysilane were coated on the surfaces of template particles via electrostatic interaction, finally the PS was dissolved in situ by modification of the reaction conditions in the same medium to form monodisperse hollow silica spheres with controlled shell thickness. Fourier transform‐infrared spectroscopy, thermogravimetric analysis, Brunauer‐Emmett‐Teller, transmission electron microscopy, and scanning electron microscope measurements were used to characterize these hollow silica spheres. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1332–1338, 2010     

一种制备单分散SiO2空心微球的新方法

在乙醇/氨水介质中, 分别以分散聚合和无皂乳液聚合方法制得的不同粒径聚苯乙烯(PS)微球为模板, 以正硅酸乙酯(TEOS)为前驱体, 通过控制介质中氨水的初始体积, 一步法制得了不同粒径的单分散SiO2空心微球. 整个过程无需添加其它溶剂溶解或高温煅烧的方法来除去模板微球. 对SiO2空心微球进行测试表征, 提出了SiO2空心微球的可能形成机制.     

Synthesis of micron-sized hollow silica spheres with a novel mesoporous shell of MCF

Micron-sized hollow silica spheres whose shells are made up of mesocellular silica foams(MCFs) have been synthesized by one-pot sol-gel method in benzene/water/P123 emulsion.The material is characterized with SEM,TEM,BET and ~(29)Si MAS NMR. The results show that the MCFs of the unique shell of hollow silica spheres were connected by large windows with a narrow distribution of～10 nm in diameter,the inner space of the hollow sphere is accessible.And the formation mechanism of the hollow silica spheres is ...