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.     

以L-苯甘氨酸衍生物为模板制备介孔SiO_2纳米空心球

用L-苯甘氨酸合成了L-苯甘氨酸衍生物阳离子两亲化合物,以其自组装体为模板,采用四乙氧基硅烷为硅源,制备了介孔SiO_2空心球.结果表明,制备的介孔SiO_2纳米粒子直径50~200nm,孔径3.8nm左右,孔道成平行排列.     

Synthesis of titania embedded silica hollow nanospheres via sonication mediated etching and re-deposition

Titania embedded silica hollow nanospheres were synthesized from sonication-mediated etching and re-deposition of silica/titania core/shell nanospheres. The designed structure of the hollow nanospheres was proved to be a key factor for the charge trapping/detrapping and resulting bistability in non-volatile organic bistable memory devices (OBDs).     

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.     

Visible light photodegradation of dyes over mesoporous titania prepared by using chrome azurol S as template

Mesoporous TiO₂ with anatase crystalline structure (MTiO₂/CAS) has been synthesized by using chrome azurol S (CAS, 2″,6″-dichloro-3,3′-dimethyl-4′-hydroxy-3″-sulfofuchson-5,5′-dicarboxylic acid) as template. It was characterized by X-ray diffraction, nitrogen adsorption/desorption, diffuse reflectance UV–visible and FT-IR spectrometry, and transmission electron microscopy. It was found that MTiO₂/CAS had substantial photocatalytic activity in the degradation of methylthionine chloride, rhodamine B, gentian violet, safranin T, methyl violet, and fuchsine basic whereas Degussa P25 (P25) had negligible photodegradation yield (<6%) under visible light irradiation.     

Granulating titania powder by colloidal route using polyelectrolytes

A new, convenient, and inexpensive approach to process and granulate titania powders by a chemical route is proposed. It is based on the use of a formulation that includes a polyanion such as poly(sodium 4-styrenesulfonate) (PSS). Such a polyelectrolyte is most often considered to achieve dispersion of oxide powders in water. Basically, it adsorbs onto the surface of particles and induces electrical and/or steric interactions between particles in the suspension, which prevents agglomeration and rapid sedimentation. The advantages of polyelectrolytes in ceramic processing is well documented in the literature to produce low viscosity suspensions that are further used to form ceramic parts. In the case of TiO2 powders, such aqueous dispersions were obtained by adding small quantities of PSS. However, when exploring the behavior of mixtures containing lower contents of dispersant, we have discovered that, well below the optimum concentration required to get stable dispersions, the polyelectrolyte can act as a binder for titania particles. This can confer cohesion to the agglomerates, which can be processed to form large size (e.g., millimeter size) spheres. This phenomenon takes place when the oxide surface carries both positive and negative electrical charges and can be explained on a simple basis involving surface chemistry. For the optimum concentration of PSS that disperses titania, a polycation such as chitosan should be added to get spheres. This simple technique is expected to receive increasing attention due its potentialities and strong advantages with respect to other granulation techniques, such as spray-drying, which are energy consuming.     

A cationic surfactant-induced selective etching strategy for the synthesis of organosilica hollow nanospheres

The simple and effective synthesis of well-defined organosilica hollow nanospheres (OHNSs) for fundamental research and practical applications is still a significant challenge. In this work, a facile “cationic surfactant-induced selective etching” strategy was developed for the fabrication of hollow thiocyanatopropyl silsesquioxanes (thiocyanatopropyl-SQ), mercaptopropyl silsesquioxane (mercaptopropyl-SQ) from cyanoethyl-SQ@thiocyanatopropyl-SQ and cyanoethyl-SQ@mercaptopropyl-SQ, respectively. The experiments demonstrated that cetyltrimethylammonium bromide (CTAB) had remarkable influence on the formation of hollow structure and could accelerate the etching process significantly. A formation mechanism initiated by the adsorption of cationic surfactant followed by the etching of inner core with NH₃·H₂O was proposed. Hollow thiocyanatopropyl-SQ and mercaptopropyl-SQ with various shell thickness could be prepared by manipulating the amount of CTAB. And large-scale OHNSs were obtained at appropriate concentration of CTAB through this strategy. Moreover, this strategy might be further extended to fabricate OHNSs with other worthy functional groups.

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A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles has been developed. The core-shell nanostructures with NH4Cl as core and TiO2·xH2O-NH4Cl as shell were prepared in nonaqueous system by the deposition on the surface of the aggregated NH4Cl crystals, which could be transformed into mesoporous anatase nanoparticles or hollow nanospheres by calcination at 500℃ or extraction with methanol, respectively. The hierarchical mesoporous nanostruc...     

微流控液滴软模板制备二氧化钛中空微球

应用微流控液滴技术合成功能材料已发展成为一个新兴领域。本文以夹流结构微流控芯片产生的微液滴作为软模板,以液滴模板界面处发生的水解反应生成二氧化钛球壳,并经后续脱核处理,制备二氧化钛中空微球。采用激光诱导荧光成像、扫描电镜等手段对微球形貌结构进行了分析表征。结果表明,通过控制微流控芯片液滴合成条件,可以得到壁厚约2 μm的二氧化钛中空微球。这种以微流控液滴为模板的合成方法简单灵活,若与其他材料改性方法相结合,有望实现对更多元、更复杂功能微球材料的制备,并进一步拓宽其在光电和催化剂材料领域的应用。     

A block copolymer micelle template for synthesis of hollow calcium phosphate nanospheres with excellent biocompatibility

We report synthesis of hollow calcium phosphate (CaP) nanospheres with high surface area by using block copolymer micelles as templates. The obtained CaP nanospheres exhibit very high biocompatibility, showing great promise for intracellular bio-applications in future.     

Reverse micelles template assisted fabrication of ZnO hollow nanospheres and hexagonal microtubes by a novel fast microemulsion-based hydrothermal method

ZnO hollow micro/nanostructures were fabricated by a novel fast hydrothermal method based on the microemulsion. The aqueous reverse micelles were used as templates and different amount of Zn²⁺ colloid was compelled to hydrolyze on its surface. Scanning electron microscopy indicates that the products grown in the solution with colloid volume concentration of 12.3 and 0.5 v.% are hollow nanospheres and hexagonal microtubes, respectively. It is believed that this difference should attribute to the initial shape of hydrolysate and the core/shell state of water/surfactant during hydrothermal treatment.     

Synthesis of ZnS hollow nanospheres with holes using different amine templates

ZnS hollow nanospheres with holes were prepared by reacting ZnSO₄ with H₂S, the sulfide source formed in the reaction of CS₂ with ethylenediamine, 1,3-propylenediamine, butylamine or 2-(2-aminoethylamino) ethanol, which also acted as a template agent, at 50°C under agitation. The shape, particle size of about 100–850 nm and hole size of about 150–600 nm of ZnS hollow nanospheres with holes were shown by SEM and TEM images. These ZnS nanospheres with β cubic ZnS phase and composed of 2–5 nm nanocrystals were characterized by XRD and HRTEM. The blue shift of maximum absorption in UV-vis displayed the effect of quantum size. The two amino groups of amine templates reacted favorably with Zn²⁺ to form uniform and relatively smooth ZnS nanospheres with holes, while hydroxyethyl played a disadvantageous role. A reasonable mechanism of hole formation by H₂S rushing out is suggested. __________ Translated from Journal of Jinan University (Natural Science), 2007, 28(1): 92–95 [译自: 暨南大学学报(自然科学版)]     

Formation of colloidal CuO nanocrystallites and their spherical aggregation and reductive transformation to hollow Cu2O nanospheres

In this work, we demonstrate that cuprous oxide Cu(2)O nanospheres with hollow interiors can be fabricated from a reductive conversion of aggregated CuO nanocrystallites without using templates. A detailed process mechanism has been revealed: (i) formation of CuO nanocrystallites; (ii) spherical aggregation of primary CuO crystallites; (iii) reductive conversion of CuO to Cu(2)O; and (iv) crystal aging and hollowing of Cu(2)O nanospheres. In this template-free process, Ostwald ripening is operative in (iv) for controlling crystallite size in shell structures and thus for precisely tuning the optical band gap energy (E(g)) of resultant semiconductor nanostructures. For the first time, a wealth of colorful Cu(2)O hollow nanospheres (outer diameters in 100-200 nm), with variable E(g) in the range of 2.405-2.170 eV, has been fabricated via this novel chemical route. Considering their unique hollow structure and facile tuning in band gap energy, the prepared Cu(2)O hollow spheres can be potentially useful for harvesting solar energy in the visible range. Possibility of fabrication of Cu-Cu(2)O nanocomposites has also been discussed.     

Water-dispersible ultrathin Au nanowires prepared using a lamellar template of a long-chain amidoamine derivative

Straight ultrathin Au nanowires (NWs) with diameters less than 2 nm were synthesized using the lamellar structure of C18AA in an organogel and its selective adsorption for specific gold surfaces. In addition, the potential to form a bilayer structure with interdigitated hydrocarbon chains enabled the production of water-dispersible Au NWs without morphological change.     

Preparation of nano and microcrystals of silver using titania xerogel matrix as template

Ag-doped TiO₂ wet gels were prepared by sol?Cgel process using a mixture of titanium isopropoxide and silver nitrate as precursor solution, with Ag:Ti molar ratio of 1:6. After drying, the titanium oxide xerogels were used as template in the preparation of nano and microcrystals of metallic silver. The porous network and the structure of the titania matrix influenced the type and distribution of silver crystal produced on the composite surface. Silver nanoparticles segregated to the surface of titania xerogel during the heating step, giving rise to nanocrystals that coalesced forming microcrystals with different shapes and faceting. The microcrystals grew on the composite surface, reaching sizes between 5 and 20 microns and self-organized of different ways. The xerogel heated at 600 °C formed by anatase, rutile and silver nanoparticles exhibited considerable photocatalytic activity to degrade methylene blue.     

Study on the morphological regulation mechanism of hollow silica microsphere prepared via emulsion droplet template

The morphology regulation of hollow silica microspheres is significant for their properties and applications. In this paper, hollow silica microspheres were formed through the hydrolysis and condensation reaction of tetraethyl orthosilicate (TEOS) at the interface of the emulsion droplet templates composed of liquid paraffin and TEOS, followed by dissolving paraffin with ethanol. The effects of various factors including the emulsifier structure and content, TEOS content, catalyst type, and the ethanol content in the continuous water phase on the particle size, shell thickness and morphology of the prepared hollow silica microspheres were studied in detail. The results show that the diffusion and contact of TEOS and water molecules as well as the hydrolysis condensation reaction of TEOS at the oil-water interface are two critical processes for the synthesis and morphological regulation of hollow silica microspheres. Cationic emulsifier with a hydrophobic chain of appropriate length is the prerequisite for the successful synthesis of hollow silica microspheres. The ethanol content in water phase is the dominant factor to determine the average diameter of hollow microspheres, which can vary from 96 nm to 660 nm with the increase of the volume ratio of alcohol-water from 0 to 0.7. The silica wall thickness varies with the content and the hydrophobic chain length of the emulsifier, TEOS content, and the activity of the catalyst. The component of the soft template will affect the morphology of the silica wall. When the liquid paraffin is replaced by cyclohexane, hollow microspheres with fibrous mesoporous silica wall are fabricated. This work not only enriches the basic theory of interfacial polymerization in the emulsion system, but also provides ideas and methods for expanding the morphology and application of hollow silica microspheres.     

Covalent organic hollow nanospheres constructed by using AIE-active units for nitrophenol explosives detection

The development of conjugated nanomaterials with high sensitivity and super-amplified quenching effect for the detection of nitrophenol explosives is still a great challenge. Herein, we developed conjugated hollow nanospheres constructed by using aggregation-induced emission(AIE) active 1,3,5-tris(4-formyl-phenyl)benzene(TFPB). The high emission hollow nanospheres with uniform size and admirable dispersiveness exhibited obvious fluorescence quenching response with the addition of nitrophenol explosives owing to the photoinduced electron transfer(PET) from the hollow nanospheres to nitrophenol explosives. The Stern-Volmer constants of hollow spheres for 2,4,6-trinitrophenol(TNP), 4-nitrophenol(NP) and 2,4-dinitrophenol(DNP) can reach 9.67×105, 3.14×10~5 and 4.8×10~4 M~(-1), respectively. Furthermore, the handy test paper coated with hollow nanospheres was prepared and showed a good response toward TNP solutions and vapor. The study provides a novel strategy to construct AIE-active conjugated hollow nanospheres for efficient nitrophenol explosives sensing.     

A porous carbon material prepared by template synthesis using Aerosil

Synthesis of a porous carbon material using Aerosil as template is suggested. The material obtained has high specific surface area (2800 m² g^?1) and high limiting sorption volume (6.2 cm³ g^?1). The porous carbon material prepared by this procedure can be used in solid-phase extraction of organic toxicants from aqueous solutions.     

Monodisperse ultrafine polystyrene nanoparticles prepared by a semicontinuous microemulsion polymerization

Monodisperse ultrafine polystyrene nanoparticles have been successfully prepared under low levels of surfactant through a novel semicontinuous microemulsion polymerization, in which the first part of monomer (St₁) is added dropwise while the subsequent supply to the polymerizing system is delivered in one potion. Polystyrene nanoparticles with number‐average diameter of 17.4 nm and polydispersity index of 1.06 were obtained using low level of surfactant/monomer weight ratio of 0.20. Influencing of parameters including amount of St₁, solid content, initiator, reaction temperature, and cosurfactant on the resultant particle size and size distribution were investigated. The mechanism of nucleation and particle growth was discussed as well. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4522–4528, 2008