模板法制备复合中空微球

本文报道以一种商品化的聚苯乙烯中空球为模板, 采用溶胀聚合技术合成了具有IPN(Inter-Penetrating Network)结构的复合中空球; 对其中的一种高分子网络进行化学改性引入所需官能团, 制得带有羧基的聚合物凝胶中空球; 利用凝胶诱导生长特性, 成功制得聚合物复合中空球. 此方法无需去除模板就可批量制备各种复合功能中空球.     

A General Route to Hollow Mesoporous Rare‐Earth Silicate Nanospheres as a Catalyst Support

Hollow mesoporous structures have recently aroused intense research interest owing to their unique structural features. Herein, an effective and precisely controlled synthesis of hollow rare‐earth silicate spheres with mesoporous shells is reported for the first time, produced by a simple hydrothermal method, using silica spheres as the silica precursors. The as‐prepared hollow rare‐earth silicate spheres have large specific surface area, high pore volume, and controllable structure parameters. The results demonstrate that the selection of the chelating reagent plays critical roles in forming the hollow mesoporous structures. In addition, a simple and low‐energy‐consuming approach to synthesize highly stable and dispersive gold nanoparticle–yttrium silicate (AuNPs/YSiO) hollow nanocomposites has also been developed. The reduction of 4‐nitrophenol with AuNPs/YSiO hollow nanocomposites as the catalyst has clearly demonstrated that the hollow rare‐earth silicate spheres are good carriers for Au nanoparticles. This strategy can be extended as a general approach to prepare multifunctional yolk–shell structures with diverse compositions and morphologies simply by replacing silica spheres with silica‐coated nanocomposites.     

Hydrothermal synthesis of hollow silica spheres under acidic conditions

It is well-known that silica can be etched in alkaline media or in a unique hydrofluoric acid (HF) solution, which is widely used to prepare various kinds of hollow nanostructures (including silica hollow structures) via silica-templating methods. In our experiments, we found that sto?ber silica spheres could be etched in generic acidic media in a well-controlled way under hydrothermal conditions, forming well-defined hollow/rattle-type silica spheres. Furthermore, some salts such as NaCl and Na(2)SO(4) were found to be favorable for the formation of hollow/rattle-type silica spheres.     

中空纳米二氧化硅微球的制备及表征

本文介绍了一种制备中空纳米二氧化硅微球的新方法。利用模板首先合成介孔纳米二氧化硅微球,再用水热反应法,成功制备了非功能化和巯基、氨基功能化中空纳米二氧化硅微球。利用透射电子显微镜,热重分析等手段对其形貌进行了表征。另外,对中空介孔纳米二氧化硅微球的形成机制进行了探讨。     

Sonochemical preparation of hollow nanospheres and hollow nanocrystals

Ceramic hollow spheres of MoS2 and MoO3 were obtained by sonochemical synthesis of MoS2 and MoO3 templated on silica nanoparticles (diameters 50-500 nm) followed by acid etching to remove the silica core. The resulting hollow materials have been characterized by elemental analysis, XPS, SEM, TEM, optical absorption, and hydrodesulfurization (HDS) studies. The TEM studies on the hollow ceramic materials indicate the formation of dispersed free spheres with a hollow core. The hollow materials obtained from thermally treated MoS2/SiO2 (450-700 degrees C) show the formation of layered MoS2 (lattice fringes approximately 6.2 A) with a wall thickness of 6-8 layers. The MoS2 hollow spheres are extremely active catalysts for the HDS of thiophene. Hollow spheres of MoO3 are prepared in a similar fashion. Surprisingly, upon heating, hollow crystals of MoO3 with sharp-edged truncated cubes containing inner voids are formed from the initial spheres.     

Tunable optical stop band of silica shell photonic crystals

In this study, optical stop band of three-dimensional silica shell photonic crystals is tuned by adjusting inner diameter and shell thickness of hollow silica spheres. The silica shell photonic crystals are fabricated by sintering crystalline arrays, which are assembled from polystyrene/silica core–shell spheres by an improved vertical deposition method. The inner diameter and the shell thickness are controlled by diameter of polystyrene spheres and concentration of tetraethoxysilane. The results of transmission spectra show that there is an evident red shift of optical stop band as the inner diameter and the shell thickness increase. The red shift of optical stop band is due to variations in the inter-planar spacing and the effective refractive index of silica shell photonic crystals, which result from the variations of the inner diameter and the shell thickness of hollow silica spheres.     

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.     

Aerosol assisted synthesis of silica/phenolic resin composite mesoporous hollow spheres

Hollow spheres of phenolic resin/silica composite are synthesized by macroscopic phase separation of a sorbitan monooleate surfactant Span 80 during aerosol-assisted spraying. The cavity can be evolved from multiple compartments to single hollow cavity with the increase of Span 80 content. The composite shell becomes mesoporous due to the release of small molecules after thermal treatment above 350 °C. After further thermal treatment at a higher temperature for example 900 °C in nitrogen or 1,450 °C in argon, the carbon/silica composite hollow spheres or crystalline silicon carbide hollow spheres are derived, respectively. Compared to the pure phenolic resin-based carbon spheres, thermal stability of the carbon-based composite spheres in air is essentially improved by the introduction of inorganic component silica. The carbon-based composite hollow spheres combine both performances of easy mass transportation through macropores and high specific surface area of mesopores, which will be promising to support catalysts for fuel cells. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hierarchically Structured Porous Films of Silica Hollow Spheres via Layer‐by‐Layer Assembly and Their Superhydrophilic and Antifogging Properties

Raspberrylike organic/inorganic composite spheres are prepared by stepwise electrostatic assembly of polyelectrolytes and silica nanoparticles onto monodisperse polystyrene spheres. Hierarchically structured porous films of silica hollow spheres are fabricated from these composite spheres by layer‐by‐layer assembly with polyelectrolytes followed by calcination. The morphologies of the raspberrylike organic/inorganic composite spheres and the derived hierarchically structured porous films are observed by scanning and transmission electron microscopy. The surface properties of these films are investigated by measuring their water contact angles, water‐spreading speed, and antifogging properties. The results show that such hierarchically structured porous films of silica hollow spheres have unique superhydrophilic and antifogging properties. Finally, the formation mechanism of these nanostructures and property–structure relationships are discussed in detail on the basis of experimental observations.     

Architecture of micron-scale hollow spheres composed of silica nanoparticles and approach to luminescent spheres

Micron-scale hollow spheres were successfully constructed with silica nanoparticles by templating of polymer spheres. Subsequently, the use of 3-aminopropyltriethoxysilane (APTES) introduces carbon and oxygen defects in the silica nanoparticles resulting from calcination of the aminopropyl group. In this approach, the template of micron-scale polymer spheres was prepared from dispersion polymerization. Subsequent St?ber process results in the formation of a silica layer attached to the polymer sphere surfaces. After calcination, the obtained micron-scale hollow silica spheres were then studied on the relationship between the particle diameter and the surface morphology. The luminescence of hollow spheres was prepared through using APTES in St?ber process, and which of related the appearance of luminescence to the APTES concentration and calcination temperature. The results of this study can provide useful information for the structure of micron-scale hollow spheres and their application to luminescent materials.     

A facile method of synthesis of asymmetric hollow silica spheres

This paper presents a "one-step" method to synthesize asymmetric hollow silica spheres. In this method, when positively charged polystyrene particles were blended with mercaptopropyltriethoxysilane and stirred at 50 °C in alkaline ethanol/water medium for a period of time, Janus or lobed asymmetric hollow silica spheres could be directly obtained, just changing the ratio of ethanol to water in the reaction medium. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to characterize the morphology and topography of the asymmetric hollow silica spheres. The formation mechanism was described in detail.     

一种新型的空心镍纳米球的合成

通过以二氧化硅粒子作为模板和金纳米粒子为表面晶种的方法制备了壳厚度可控的镍空心球。采用TEM﹑XRD对二氧化硅/镍复合球和镍空心球进行了表征和研究。结果表明镍纳米壳是由似针状的面心立方的镍纳米粒子构成的，碱溶液处理过程不影响镍纳米壳的形貌。高温处理显示镍空心球具有良好的热稳定性。     

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     

以手性两亲小分子自组装体为模板制备介孔二氧化硅空心球

合成了手性阳离子型两亲性小分子化合物,利用圆二色谱分析了其在水中形成的自组装体的结构;以该化合物的自组装体为模板,在正丙醇和氨水的混合溶剂中制备得到了介孔二氧化硅空心球;利用扫描电镜、透射电镜、X射线衍射仪以及氮气吸附-脱附试验装置分析了二氧化硅空心球的形貌及孔结构.结果表明,两亲性小分子在水中形成的自组装体呈现手性堆积;合成的介孔二氧化硅空心球的直径约为600~800nm,壁厚约为100~150nm,其孔道垂直于球的表面,孔径约为3.0nm,比表面积约为306m2·g-1.正丙醇作为模板控制二氧化硅空心球的空腔尺寸和形貌,而两亲性小分子的自组装体作为模板控制放射状孔道的形貌和尺寸.     

Preparation of hollow silica microspheres with controlled shell thickness in supercritical fluids

This article presents a novel route to prepare hollow silica microspheres with well-defined wall thickness by using cross-linked polystyrene (PS) microspheres as templates with the assistance of supercritical carbon dioxide (SC-CO₂). In this approach, the cross-linked PS templates can be firstly prepared via emulsifier-free polymerization method by using ethylene glycol dimethacrylate or divinylbenzene as cross-linkers. Then, the silica shell from the sol–gel process of tetraethyl orthosilicate (TEOS) which was penetrated into the PS template with the assistance of SC-CO₂ was obtained. Finally, the hollow silica spheres were generated after calcinations at 600 °C for 4 h. The shell thickness of the hollow silica spheres could be finely tuned not only by adjusting the TEOS/PS ratio, which is the most frequently used method, but also by changing the pressure and aging time of the SC-CO₂ treatment. Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscope were used to characterize these hollow silica spheres.     

Chemical‐Template Synthesis of Micro/Nanoscale Magnesium Silicate Hollow Spheres for Waste‐Water Treatment

Micro/nanoscale magnesium silicate hollow spheres were synthesized by using silica colloidal spheres as a chemical template in one pot. The hollow spherical structure, consisting of well‐separated nanoscale units, was microscale as a whole and could be easily handled in solution. The as‐synthesized magnesium silicate hollow spheres with large specific surface area showed availability for the removal of organic and heavy‐metal ions efficiently from waste water. Importantly, the micro/nanoscale magnesium silicate hollow spheres that had adsorbed organic pollutants could be regenerated by calcination and used repeatedly in pollutant removal. Magnesium silicate hollow spheres synthesized by a scaled‐up chemical template method may have potential applications in removing cationic dyes and heavy‐metal ions from waste water.     

Fabrication of triple-shelled hollow spheres with optical properties via RAFT polymerization

<正>The triple-shelled hollow spheres with optical properties were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization.After removal the core templates of the poly(styrene),the hollow silica spheres were obtained.The coating process of poly(methyl methacrylate)(PMMA) on the hollow silica spheres surface via surface RAFT polymerization was performed subsequently.The polymers coated on the hollow spheres surfaces were end-functionalized by trithiocarbonate,and they were used as RAFT agent to proceed the chain extension polymerization using Tb complex as monomer.The samples were characterized by FT-IR,SEM and luminescence spectroscopy respectively.The results indicated that the triple-shelled hollow spheres had been prepared successfully and the average diameter of the hollow core was about 1μm.     

海藻酸改性的中空SiO2微球的简易制备及应用

以CaCO3为模板,正硅酸四乙酯（TEOS）为硅源,用比较简单的方法制备了中空SiO2;然后将海藻酸钠嫁接在氨基化的中空SiO2表面;再利用海藻酸盐与钙离子的作用,在中空SiO2表面形成一个凝胶化层,制得海藻酸盐凝胶化的中空SiO2微球,粒径为1~2 μm。 采用FTIR、XRD、SEM、TEM和TGA等测试技术对微球进行表征。 此微球成功地用于柔红霉素的载负和缓释,最大载负率和载药量分别为55.6%和27.8%;缓释结果表明,海藻酸盐凝胶化层的存在,能更有效控制柔红霉素缓慢的释放,这种凝胶化载体对药效强、毒性较大的药物有潜在的临床应用前景。     

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.     

One-pot synthesis of bimetallic Fe/Co incorporated silica hollow spheres with superior peroxidase-like activity

Mesoporous silica hollow spheres with a homogenous and high content distribution of Fe and Co were synthesized by a facile one-pot hydrothermal process. The sub-nanometer bimetallic components inside the silica framework facilitate the stable fixation and the open accessibility to active sites. The co-doped Fe/Co in the spheres showed excellent peroxidase-like activity and much higher catalytic performance than their monometallic-supported spheres. The synergistic effect between Fe and Co promotes the continuous formation of functional radicals during the oxidation process and thus accelerates the reaction rate. When used for colorimetric detection of hydrogen peroxide (H₂O₂), the Fe/Co incorporated silica hollow spheres show the capability of detection of H₂O₂ in a wide range (10-250 µmol/L) and with the low detection limit of 0.012 ppm.