Highly ordered three-dimensional macroporous carbon spheres for determination of heavy metal ions

An effective voltammetric method for detection of trace heavy metal ions using chemically modified highly ordered three dimensional macroporous carbon spheres electrode surfaces is described. The highly ordered three dimensional macroporous carbon spheres were prepared by carbonization of glucose in silica crystal bead template, followed by removal of the template. The highly ordered three dimensional macroporous carbon spheres were covalently modified by cysteine, an amino acid with high affinities towards some heavy metals. The materials were characterized by physical adsorption of nitrogen, scanning electron microscopy, and transmission electron microscopy techniques. While the Fourier-transform infrared spectroscopy was used to characterize the functional groups on the surface of carbon spheres. High sensitivity was exhibited when this material was used in electrochemical detection (square wave anodic stripping voltammetry) of heavy metal ions due to the porous structure. And the potential application for simultaneous detection of heavy metal ions was also investigated.     

Fabrication of hollow silica spheres in an ionic liquid microemulsion

Hollow silica spheres have been successfully synthesized by using the ionic liquid microemulsion droplets as the template. The morphology and microstructures of the silica spheres were investigated by scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM), and Nitrogen adsorption-desorption measurements. The obtained images showed that the average size of the silica spheres was almost between 150 and 300 nm. The Nitrogen adsorption-desorption investigation on the silica spheres indicated the amorphous structure on the interface. Both of these two results provide us new insights into this novel template and hollow silica spheres were for the first time prepared free of additional acid and alkali conditions. The possible mechanism for the formation of silica spheres has been put forward and discussed in details.     

Experimental and numerical studies on liquid bridge formed among three spheres

Static characteristics and dynamic strength of a liquid bridge formed between vertically arranged two spheres and among three spheres were experimentally and numerically investigated. The existences of minimum and maximum bridge volumes were experimentally determined. The shapes at intermediate volumes were successfully simulated by Young-Laplace equation. Most of liquid bridges at the minimum volumes in case of three spheres were formed upon not the lower spheres but the upper sphere under narrow sphere gap. The tensile strength of the bridge formed among three spheres is larger than that between two spheres at the faster stretching speed. The effective dimensionless sphere gap for the strength was below 0.2. The simulated flow patterns within dynamical liquid bridges between vertically arranged two spheres account for the drastic decrease in the adhesive force between spheres.Authors gratefully thank Professor Isao Sekiguchi for supporting the experiment apparatus for measuring a dynamic adhesive force and Emeritus professor Shigeki Toyama for advising this paper.     

One-step strategy for synthesis of yolk–shell silica spheres using trisiloxane-tailed ionic liquids as a template

Yolk–shell silica spheres consisting of a core and an outer shell were prepared by a one-step method using a new class of eco-friendly templates, trisiloxane-tailed surface active ionic liquids. The effects of pH, calcination, and template concentration were investigated in detail. Our results showed that yolk–shell silica spheres could be obtained only in alkaline conditions when using trisiloxane-tailed ionic liquids as templates. The particle diameter, core diameter, dimension of void space, and shell thickness, which we measured by transmission electron microscopy and nitrogen adsorption–desorption techniques, could be tuned by precisely varying the template concentration. The organosilicon component of the ionic liquid template contributes to the reaction during the formation of yolk–shell nanostructures, which leads to a firm silica sphere skeleton resulting in essentially identical morphology and void structure before and after calcination. This investigation provides a convenient approach to fabricate yolk–shell silica spheres, which may expand the application of organosilicon ionic liquids in the field of nanomaterials and could be expected to generate tailor-made yolk–shell silica with functionality in both the core and shell.     

Colloidal and transparent opal-matrix nanocomposites filled with europium-doped silica sols

Three-dimensional ordered opal-matrix composites filled with europium-doped silica sols have been produced using methods of colloid chemistry. According to elemental analysis data, the Eu concentration in the nanocomposites was ～30 ppm. A uniform europium distribution over the tetrahedral and octahedral pores of the 3D opal matrix was ensured by repeatedly filling the opal pores with silica sols doped with europium salts or europium oxide. Varying high-temperature annealing conditions, one can control the microstructure of 3D ordered nanocomposites, producing opaline and transparent photonic crystals. The microstructure of opal photonic crystals has the form of an ordered fcc lattice of amorphous silica spheres, whose tetrahedral and octahedral pores are filled with mesoporous europium-doped glass. Partial sintering of the silica spheres and mesoporous glass in transparent photonic crystals results in a periodic arrangement of quantum dots enriched in Eu-doped silica.     

Modified spontaneous emission of organic molecules in-filled in inverse opals

Inverse opals were prepared by replication of colloidal crystal templates made from silica spheres 298 nm in diameter. The air between the silica spheres was filled with the mixture of the monomer poly(methyl methacrylate) (PMMA) and the organic molecule Alq3 that can be subsequently polymerized. After removing the silica sphere templates, the photonic bandgap effect on the spontaneous emission of Alq3 were investigated. The dip in the fluorescence spectrum was interpreted in terms of redistribution of the photon density of states in the photonic crystal.     

Stimulated light scattering in synthetic opal filled with dielectrics

We have studied characteristics of stimulated light scattering in synthetic opal crystals made up of silica spheres. This type of light scattering results from interaction between pulsed laser radiation and dielectric nanoparticles, such as silica (SiO₂) spheres in the structure of synthetic opal. The Stokes shift in the scattered radiation spectrum was 0.4–1.0 cm^?1. The Stokes shift was determined as a function of scattering geometry, sphere diameter, sample temperature, and the type of dielectric in the opal pores. The results are of interest for assessing the size of nanoparticles in spatially ordered inorganic structures.     

反应介质对二氧化硅在碳球表面包覆效果的影响

为了改善碳球表面惰性,利用溶胶-凝胶法在碳球表面包覆二氧化硅,考察了介质条件对包覆效果的影响。通过场发射扫描电子显微镜和透射电子显微镜等手段对不同介质中得到的样品进行对比分析表征。结果表明,碱性介质更有利于二氧化硅在碳球表面的包覆,所得复合物球表面光滑、包覆层厚且厚度均一,焙烧除去碳球核后得到空心二氧化硅球,并分析了碳球表面二氧化硅的包覆机理。     

Structured Porous Materials via Colloidal Crystal Templating: From Inorganic Oxides to Metals

The formation of nanostructured materials by using colloidal crystals as templates is a relatively new but rapidly growing area of materials science. Colloid crystalline templates are three‐dimensional close‐packed crystals of submicrometer spheres, whose long‐ranged ordered structure is replicated in a solid matrix, to yield materials with ordered pores. These materials hold promise for use as photonic crystals, advanced catalysts, and in a variety of other applications. Here we review the wide range of materials that have been made following the original synthesis of structured porous silica. This method has been recently modified to produce porous metals.     

Titania nanotube/hollow sphere hybrid material: Dual-template synthesis and photocatalytic property

Inspired by the complicated structure of natural substances, we designed and fabricated nanotube/hollow sphere hybrid structured functional anatase titania material. Cellulosic substance (commercial filter paper) was chosen as nanotube template while silica and polystyrene colloidal microspheres with different diameters were employed as hollow sphere templates. The ultrathin nature of titania layer enabled faithful replication of the nanoscopic structural details of both the template substances. The microsphere and cellulose templates were removed by calcination for polystyrene microsphere template case, and further alkali treatment was carried out to dissolve away the silica component for silica microsphere template case. The obtained anatase titania nanotubes were decorated with nanoscale titania hollow spheres with wall thickness of about 7.5 nm. The resulted hybrid materials exhibited similar but superior photocatalytic efficiency compared with simple titania nanotube structured materials due to the higher surface area endowed by the complex highly porous structure.     

Moduli of ordered polymer composites prepared by colloidal crystallization of nano- and micro-SiO2 spheres in crosslinked methacrylate resins

The extraordinary mechanical performance of nanomaterials found in nature has been attributed to the ordered arrangement of the components. Here, nano- and mico-composites containing either ordered or disordered arrangement of the spheres were compared. The nano- and micro-composites were formed using 19–45 vol% silica in crosslinked resins of triethylene glycol dimethacrylate (TEGDMA) and methyl methacrylate (MMA), in weight ratios TEGDMA/MMA of 100/0, 80/20 or 60/40. The silica nanoparticles, with sizes of 250, 500 and 1000 nm diameter, were silanated with methacryloxypropyl trimethoxysilane (MPS), MPS-SiO₂, to promote bonding to the resin. The ordered nano- or micro-composites were obtained by colloidal crystallization and formed face-centered cubic arrays. Disorder was achieved by mixing two particle sizes or by addition of a coinitiator, dimethylaminoethyl methacrylate (DMAEMA). Ordered nano- or micro-composites had moduli 30% higher than similar composites in which disordered was introduced by mixing two size spheres, at the same loading, for all resin compositions. The greatest improvement occurred at the highest packing density of the spheres, 45 vol%. When disorder was introduced by addition of DMAEMA, the mechanical properties of the ordered and disordered composites were similar, since local but not long-range regions of order was also achieved in the latter case.     

正硅酸乙酯的水解缩聚反应及多孔SiO_2粉体的制备

详细描述了正硅酸乙酯的水解缩聚反应过程,简要介绍了影响反应过程的相关因素;综述了气凝胶和有序介孔SiO2材料这两种以该反应为基础的、具有代表性的多孔SiO2粉体的制备,特别是对多孔SiO2微球的制备进行了比较。指出以正硅酸乙酯的水解缩聚反应为基本过程制得的SiO2粉体中无序排列的孔是普遍存在的,如在反应过程中引入模板剂或采用其它手段,无序排列的孔可变为有序的。     

溶剂处理对沥青球氧化稳定化的影响研究

研究了溶剂处理时间、温度等条件对石油沥青球和煤沥青球的收率、氧化破损率及氧化稳定化效果的影响,结果表明：在室温下用烷烃类浸泡沥青球,可以有效地除去沥青球中的萘和轻组份,打通氧气向内扩散的通道,缩小沥青球表面和呐部氧化反应程度差别,促进沥青球的快速均匀不熔化;提高溶剂处理温度,容易刻蚀球表面,影响球的外观和强度;较低软化点的石油沥青球比煤沥青球比煤沥青球表面更易于刻蚀更难于氧化稳定化。     

Sputtering fabrication of large scale ZnO nanobowl arrays using colloidal crystal templates

Ordered ZnO nanobowl arrays over cm2 areas were prepared by magnetron sputtering using the self-assembled polystyrene spheres arrays as templates. The process started with self-assembled sedimentation of there-dimensional (3D) hexagonal polystyrene sphere arrays. By depositing ZnO within the interstitials of 3D polystyrene colloidal crystal templates using magnetron sputtering, large-area ordered ZnO nanobowl sheets were prepared after removing the spheres by annealing. The whole nanobowl sheet could be lifted off, leaving accidentally observed inverse opal structures. The sizes of the nanobowls could be controlled by the size of the polystyrene spheres, the height of nanobowl sheets could be altered by changing sputtering parameters.     

天然石墨球-热解炭核壳结构的制备及电化学性能研究

通过化学气相沉积的方法,以乙炔为碳源,天然石墨球为原料,采用不同流化床CVD工艺和不同的反应时间,制备出具有光滑表面或颗粒状热解炭包覆层的核-壳构型改性天然石墨球.改性天然石墨球的核体是具有高度有序石墨结构的天然石墨,而壳体是无序结构的热解炭.与天然石墨球相比,具有核-壳结构的改性天然石墨球的首次库仑效率和循环性能都得到显著改善.尤其是具有颗粒状热解炭包覆层的改性石墨具有优异的循环性能,在41次循环后其放电容量仍为首次容量的84%,这一改善归因于表面沉积的颗粒状热解炭有效地降低了改性天然石墨颗粒之间的接触电阻和增加了接触面积.     

Third-order optical nonlinearity of cadmium sulfide nanoparticles loaded in mesostructured silica materials

Cadmium sulfide nanoparticles have been successfully incorporated in three forms of CTAB-templated mesoporous silica materials: one is the mesoporous silica spheres suspended in ethanol solution, the other is the mesoporous silica spheres spin-coated on glass slide, and the third is the dip-coated mesoporous silica thin film. The mesostructures were characterized by XRD and TEM, respectively. Linear optical properties were investigated using UV-visible spectra, and the diameter of the incorporated CdS nanoparticles was measured to be around 3.1 nm. Z-scan technique manifested that these three composites exhibited distinct third-order optical nonlinearities due to the different preparation techniques. Reverse saturation absorption could be detected in the CdS-loaded mesoporous silica spheres suspended in solution, while those dispersed on glass slide presented saturation absorption. The difference in nonlinear absorption of the two mesoporous silica sphere samples could be attributed to defect-related transitions. On the contrary, the CdS-loaded mesoporous silica thin film showed self-defocusing behavior with no nonlinear absorption signals. Compared to that of the CdS nanoparticles with larger size previously reported, the intrinsic microscopic third-order nonlinear optical susceptibility of those incorporated in CTAB-templated mesoporous thin film was increased as predicted by the quantum theory, and the third-order optical nonlinearity was further determined to arise from intraband transitions induced by quantum confinement.     

Spherical gradient-index polymer lens with low spherical aberration

A sphere lens with a spherical gradient index (GRIN) was prepared by the modified suspension polymerization technique. GRIN spheres with quadratic- and linear-index distributions were obtained by two different methods to confirm the effect of the GRIN profile on the focusing property of the sphere lens. It was confirmed in both theory and experiment that the spherical aberration of such GRIN spheres was remarkably decreased compared with that of a homogeneous sphere.     

Preparation and use of chemically modified MCM-41 and silica gel as selective adsorbents for Hg(II) ions

Adsorbents for Hg(II) ion extraction were prepared using amorphous silica gel and ordered MCM-41. Grafting with 2-(3-(2-aminoethylthio)propylthio)ethanamine was used to functionalize the silica. The functionalized adsorbents were characterized by nitrogen adsorption, X-ray diffraction, 13C MAS NMR spectroscopy and thermogravimetric analysis. The adsorption properties of the modified silica gel and MCM-41 were compared using batch method. The effect of pH, stirring time, ionic strength and foreign ions were studied. The extraction of Hg(II) ions occurred rapidly with the modified MCM-41 and the optimal pH range for the extraction by the modified materials was pH 4-7. Foreign ions, especially Cl- had some effect on the extraction efficiency of the modified silica gel and the modified MCM-41. The adsorption behavior of both adsorbents could be described by a Langmuir model at 298 K, and the maximum adsorption capacity of the modified silica gel and MCM-41 at pH 3 was 0.79 and 0.70 mmol g(-1), respectively. The modified MCM-41 showed a larger Langmuir constant than that of the modified silica gel, indicating a better ability for Hg(II) ion adsorption. The results indicate that the structure of the materials affects the adsorption behavior. These materials show a potential for the application as effective and selective adsorbents for Hg(II) removal from water.     

基于压浮原理的单晶硅球密度比较测量方法研究

为了克服单晶硅球密度测量静力称重法精度受液体表面张力的影响,研究了压浮法进行单晶硅球密度精密比较测量方法和测量系统。在一定的温度下,调节压力,利用液体压缩系数控制液体密度使标准单晶硅球和被测单晶硅球稳定悬浮于工作液体中,通过温度、压力和悬浮高度的测量,计算出二者之间的密度差值。通过双层控温系统保证了液体温度长期波动在±0.25 mK内,利用标准单晶硅球在不同温度-压力悬浮条件线性关系计算出液体压缩系数。试验证明,压浮法测量装置实现了单晶硅球密度差值的精密测量,标准测量相对不确定度为2×10^-7。     

Fabrication of hollow silica spheres and their application in polyacrylate film forming agent

Polystyrene (PS)/silica core/shell spheres were fabricated using mono-dispersed PS as templates by hydrolysis and condensation of two different silica precursors. The PS cores of PS/silica core/shell spheres were dissolved subsequently in the tetrahydrofuran medium to form mono-dispersed hollow silica spheres. The structures and morphologies of hollow silica spheres were characterized by scanning electron microscopy and transmission electron microscopy. Then, polyacrylate/hollow silica composite film forming agents were prepared via physical blending of polyacrylate and two different hollow silica spheres, and the water vapor permeability of their films were compared. The results showed that the structure of hollow silica spheres were very typical and obvious. The silica shell was continuous and uniform using tetraethylorthosilicate as precursor, which was accumulated by many silica seeds with size of 10–20 nm, and the thickness of silica shell was about 16.7 nm. However, the hollow silica spheres using tetraethylorthosilicate and vinyl triethoxysilane as precursors had mesoporous structure in the shell. The introduction of hollow silica spheres could significantly improve the water vapor permeability of polyacrylate film. At last, a possible mechanism for the formation of hollow silica spheres was proposed and the process of water vapor through polyacrylate/hollow silica composite films was modeled.