SnO2 hollow spheres:Polymer bead-templated hydrothermal synthesis and their electrochemical properties for lithium storage

SnO2 hollow spheres have been synthesized via a facile hydrothermal method using sulfonated polystyrene beads as a template followed by a calcination process in air.X-ray diffraction,scanning electron microscopy,and transmission electron microscopy show that the as-obtained SnO2 hollow spheres have a wall thickness of about 50 nm,and consist of nanosized SnO2 particles with a mean diameter of about 15 nm.Electrochemical measurements indicate that the SnO2 hollow spheres exhibit improved electrochemical performance in terms of specific capacity and rate capability in comparison with commercial SnO2 when used as anode materials for lithium-ion batteries.The enhanced performance may be attributed to the spherical and hollow structure,as well as the building blocks of SnO2 nanoparticles.     

Facile fabrication and optical property of hollow SnO2 spheres and their application in water treatment

Hollow SnO(2) spheres with smooth surface have been fabricated by a low temperature template-free solution phase route via self-assembly of small nanocrystalline particles. These hollow spheres have a very thin shell thickness of about 10 nm and are built from SnO(2) nanocrystals of an average size of 5.3 nm. The evacuation behavior of inside-out Ostwald ripening can be used to explain the formation of hollow spheres according to results of time-dependent reactions. The cathodoluminescence spectrum indicates a blue shift of the band gap emission peak of SnO(2), originating from quantum confinement effect due to the nanoscale size of SnO(2) particles. The as-prepared SnO(2) hollow spheres were also found to exhibit excellent performance in wastewater treatment.     

TiO2/SnO2复合空心球在染料敏化太阳能电池中的应用

采用模板辅助法制备了SnO2/TiO2复合空心球,样品直径为1.5~4.0μm,比表面积达到了92.9 m^2·g^-1,复合空心球表现出优越的光散射性能.以这种复合空心球作为染料敏化太阳能电池的光阳极,电池的光电转换效率可达到7.72%,高于SnO2微米球(2.70%)和TiO2微米球(6.26%).此外,以锐钛矿型TiO2纳米晶作为底层,SnO2/TiO2复合空心球作为光散射层制备的双层结构光阳极,电池光电转换效率进一步提升至8.43%.     

Formation of SnO2 hollow nanospheres inside mesoporous silica nanoreactors

We report an interesting approach for efficient synthesis of SnO(2) hollow spheres inside mesoporous silica "nanoreactors". The as-prepared products are shown to have a uniform size distribution and good structural stability. When evaluated for their lithium storage properties, these SnO(2) hollow spheres manifest improved capacity retention.     

SnO2 hollow nanospheres assembled by single layer nanocrystals as anode material for high performance Li ion batteries

SnO₂ hollow nanospheres were successfully synthesized via a facile one-step solvothermal method.Characterizations show that the as-prepared SnO₂ spheres are of hollow structure with a diameter at around 50 nm,and especially,the shell of the spheres is assembled by single layer SnO₂ nanocrystals.The surface area of the material reaches up to 202.5 m²/g.As an anode material for Li ion batteries,the sample exhibited improved electrochemical performance compared with commercial SnO₂ particles.After cycled at high current rate of 0.5 C,1 C and 0.5 C for 20 cycles,respectively,the electrode can maintain a capacity of 509 mAh/g.The suitable shell thickness/diameter ratio endows the good structural stability of the material during cycling,which promises the excellent cycling performance of the electrode.The large surface area and the ultra thin shell ensure the high rate performance of the material.     

Use of carbonaceous polysaccharide microspheres as templates for fabricating metal oxide hollow spheres

A general method for the synthesis of metal oxide hollow spheres has been developed by using carbonaceous polysaccharide microspheres prepared from saccharide solution as templates. Hollow spheres of a series of metal oxides (SnO2, Al2O3, Ga2O3, CoO, NiO, Mn3O4, Cr2O3, La2O3, Y2O3, Lu2O3, CeO2, TiO2, and ZrO2) have been prepared in this way. The method involves the initial absorption of metal ions from solution into the functional surface layer of carbonaceous saccharide microspheres; these are then densified and cross-linked in a subsequent calcination and oxidation procedure to form metal oxide hollow spheres. Metal salts are used as starting materials, which widens the accessible field of metal oxide hollow spheres. The carbonaceous colloids used as templates have integral and uniform surface functional layers, which makes surface modification unnecessary and ensures homogeneity of the shell. Macroporous films or cheese-like nanostructures of oxides can also be prepared by slightly modified procedures. XRD, TEM, HRTEM, and SAED have been used to characterize the structures. In a preliminary study on the gas sensitivity of SnO2 hollow spheres, considerably reduced "recovery times" were noted, exemplifying the distinct properties imparted by the hollow structure. These hollow or porous nanostructures have the potential for diverse applications, such as in gas sensitivity or catalysis, or as advanced ceramic materials.     

Synthesis and antibacterial property of hollow SiO2/Ag nanocomposite spheres

This paper presents a novel and facile method to fabricate hollow silica/sliver (SiO(2)/Ag) nanocomposite spheres. In this approach, the monodisperse hollow SiO(2) colloids bearing quantenary ammonium groups were prepared by dispersion polymerization combined sol-gel process and used as templates. The Ag(+) ions were first adsorbed onto the surfaces of the hollow SiO(2) beads via electrostatic interaction and then in situ reduced by the deprotonated silanol groups of the hollow SiO(2) beads, no extra reducing agents or catalysts were added during the reduction process. TEM, SEM and EDX analyses indicated that Ag nanoparticles were successfully deposited onto the surfaces of hollow SiO(2) beads. Some influencing parameters, such as the amount of quantenary ammonium groups in the inner wall of hollow SiO(2) colloids, Ag(+) ions concentration and reaction temperature, on the deposition of Ag nanoparticles onto SiO(2) colloids were investigated. Preliminary antibacterial tests indicated that these hollow nanocomposite spheres showed excellent antibacterial ability.     

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.     

Preparation of SiO2@polystyrene@polypyrrole sandwich composites and hollow polypyrrole capsules with movable SiO2 spheres inside

In this paper, we describe a flexible method for preparing conducting building blocks: SiO2@polystyrene@polypyrrole sandwich multilayer composites and hollow polypyrrole (PPy) capsules with movable SiO2 spheres inside. First, SiO2@polystyrene (PS) core/shell composites were synthesized, and then SiO2@PS@PPy sandwich multilayer composites were prepared by chemical polymerization of pyrrole monomer on the surface of SiO2@PS composites. Furthermore, hollow polypyrrole capsules with movable SiO2 spheres inside were obtained after removal of the middle PS layer. The diameter of sandwich multilayer composites could easily be controlled by adjusting the dosage of pyrrole monomer. The conductivities of composites increased with the increase of PPy content. After the insulating PS layer was selectively etched, the conductivities of hollow capsules with movable SiO2 spheres inside were much higher than those of the corresponding sandwich multilayer composites.     

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.     

Synthesis of silica/carbon-encapsulated core-shell spheres: templates for other unique core-shell structures and applications in in situ loading of noble-metal nanoparticles

Silica@carbon core-shell spheres have been synthesized via a hydrothermal carbonization procedure with glucose as the carbon precursor and silica spheres as the cores. Such SiO(2)@C core-shell spheres can be further used as templates to produce SiO(2)@C@SiO(2), and SiO(2)@SiO(2) spheres with a vacant region in two SiO(2) shells, noble-metal nanoparticle loaded SiO(2)@C core-shell spheres, and hollow carbon capsules through different follow-up processes. The obtained core-shell materials possess remarkable chemical reactivity in reducing noble-metal ions to nanoparticles, e.g., platinum. These unique core-shell spherical composites could find applications in catalyst supports, adsorbents, encapsulation, nanoreactors, and reaction templates.     

Synthesis, characterization, and optical properties of well-defined N-doped, hollow silica/titania hybrid microspheres

Well-defined nitrogen-doped, hollow SiO2/TiO2 hybrid spheres were successfully prepared through a two-step sol-gel synthesis combined calcination process using triethylamine as the nitrogen source. In this approach, polystyrene (PS)/silica microspheres were first synthesized. Subsequently, the amine-treated PS/SiO2/TiO2 hybrid spheres were obtained by sol-gel method. Finally, the elimination of the PS core, nitrogen-doping process, and crystallization of amorphous TiO2 were simultaneously conducted in the calcination process to acquire the final products. The as-prepared hybrid spheres were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. The results of XRD, FTIR, and XPS spectra indicated that nitrogen was really doped into the anatase TiO2 shell and confirmed that most nitrogen dopants might be present in the chemical environments of N-Ti-O and Ti-N-O. It was found that the absorption shoulder of nitrogen-doped hollow SiO2/TiO2 hybrid spheres vastly shifted to the visible region up to around 530 nm. The photoluminescence (PL) bands showed spectral lines at about 421, 472, and 529 nm, which were attributed to the self-trapped excitons, F and F+ centers. Moreover, the intensity of the PL spectra band of hollow SiO2/TiO2 hybrid spheres increased with as the amount of titanium tetrabutoxide (TBOT) precursor increased. However, the doping of nitrogen into hollow SiO2/TiO2 hybrid spheres led to the drastic quenching of photoluminescence because of the increase in the separation efficiency of the photoinduced electron and hole pairs.     

利用具有核壳结构的SiO2@PPy粒子制备SiC空心球

碳化硅(SiC)材料具有耐高温、 耐酸碱腐蚀和高机械强度等优异性能, 因此, 许多研究者都致力于制备优良的SiC材料以取代传统材料用作苛刻条件下催化剂的载体材料[1～4]. 研究结果表明, 具有高比表面积和空心核结构的载体材料可以负载更多的异质催化剂, 从而提高催化剂的催化性能. 因此, 制备同时具有高比表面积和空心核结构的SiC材料具有重要的应用价值. 传统的碳热还原反应、 自蔓延高温合成、 聚合物热分解等方法都不适合制备具有独特结构形貌的SiC材料[5～8]. 近年来, Ledoux等[1～4, 9]采用形状记忆合成(Shape memory synthesis)方法将不同形貌的固相碳材料与气相SiO蒸气反应, 成功地制备了不同形状的SiC材料, 比表面积在20～100 m2/g之间. Vix-Guterl等[10- 11]采用反应复制技术(Reactive replica technique)从C/SiO2材料制备了微米级的管状SiC材料. 另外, Tang等[12]采用水热合成法得到了纳米级的SiC空心球, 但产率不高. 本文利用具有核壳结构的SiO2@PPy粒子在1 300 ℃进行碳热还原反应, 成功制备同时具有较高比表面积和空心核结构的SiC空心球材料.     

TiO2 and SnO2@TiO2 hollow spheres assembled from anatase TiO2 nanosheets with enhanced lithium storage properties

TiO(2) and SnO(2)@TiO(2) hollow spheres assembled from anatase TiO(2) nanosheets with exposed (001) high-energy facets are constructed via a templating approach, and the as-prepared samples exhibit enhanced lithium storage properties.     

Rapid Fabrication of Hollow SiO2 Spheres with Novel Morphology

The hydrolysis of tetraethoxysilane (TEOS) occurred on the surface of poly(methyl methacrylate) (PMMA) microshperes immediately after these microshperes were prepared in TEOS. Micron-sized hollow SiO2 spheres were obtained by calcination of the coated PMMA microshperes. It was found that the final hollow spheres were constituted by small SiO2 particles.     

Water‐dispersible Hollow Microporous Organic Network Spheres as Substrate for Electroless Deposition of Ultrafine Pd Nanoparticles with High Catalytic Activity and Recyclability

Microporous organic networks (MONs) have been considered as an ideal substrate to stabilize active metal nanoparticles. However, the development of highly water‐dispersible hollow MONs nanostructures which can serve as both the reducing agent and stabilizer is highly desirable but still challenging. Here we report a template‐assisted method to synthesize hollow microporous organic network (H‐MON) spheres using silica spheres as hard template and 1,3,5‐triethynylbenzene as the building blocks through a Glaser coupling reaction. The obtained water‐dispersible H‐MON spheres bearing sp‐ and sp²‐hybridized carbon atoms possess a highly conjugated electronic structure and show low reduction potential; thus, they can serve as a reducing agent and stabilizer for electroless deposition of highly dispersed Pd clusters to form a Pd/H‐MON spherical hollow nanocomposite. Benefitting from their high porosity, large surface area, and excellent solution dispersibility, the as‐prepared Pd/H‐MON hollow nanocomposite exhibits a high catalytic performance and recyclability toward the reduction of 4‐nitrophenol.     

Size-controllable one-dimensional SnO2 nanocrystals: synthesis, growth mechanism, and gas sensing property

Single crystalline one-dimensional (1-D) SnO(2) nanocrystals with controllable sizes, including the diameter and the aspect ratio, were synthesized by modulating the precursor concentration, reaction time and temperature via a solution method. By regulating the growth in a kinetic regime, a higher temperature range (220-240 degrees C) was beneficial to the growth of SnO(2) nanowires, while reactions below 220 degrees C only resulted in nanorods or even nanoparticles. The aggregates of SnO(2) nanocrystals in the forms of hollow spheres and dendrites were observed as the intermediates for the nanowires. Based on the TEM and SEM observations, the growth mechanism is discussed from the viewpoints of the nature of the reverse micelles and the crystal habit of rutile SnO(2). CO gas sensing measurements were also carried out for SnO(2) nanocrystals with different assembly styles. The results indicate that the sensitivity had close correlation to the specific surface area of the nanocrystals.     

A magnesium carbonate recyclable template to synthesize micro hollow structures at a large scale

A facile strategy by using magnesium carbonate as the recyclable template has been developed to synthesize a variety of uniform inorganic hollow structures whose composition, size and shape can be readily modulated to generate interesting structures such as TiO(2), Al(2)O(3), SiO(2), Gd(2)O(3) and NiO microtubes and TiO(2), SiO(2) hollow microboxes.     

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.     

Low‐Temperature Facile Template Synthesis of Crystalline Inorganic Composite Hollow Spheres

This report presents a facile approach for the low‐temperature synthesis of crystalline inorganic‐oxide composite hollow spheres by employing the bulk controlled synthesis of inorganic‐oxide nanocrystals with polymer spheres as templates. The sulfonated polystyrene gel layer can adsorb the target precursor and induce inorganic nanocrystals to grow on the template in situ. The crystalline phase and morphology of the composite shell is tunable. By simply adjusting the acidity of the titania sol, crystalline titania composite hollow spheres with tunable crystalline phases of anatase, rutile, or a mixture of both were achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate) composite hollow spheres. The traditional thermal treatment for crystallite transformation is not required, thus intact shells can be guaranteed. The combination of oxide properties such as high refractive index, high dielectric constant, and catalytic ability with the cavity of the hollow spheres is promising for applications such as opacifiers, photonic crystals, high‐κ‐gate dielectrics, and photocatalysis.