Fabrication of functional hollow carbon spheres with large hollow interior as active colloidal catalysts

In this study,we have established a facile method to synthesize functional hollow carbon spheres with large hollow interior,which can act as active colloidal catalysts.The method includes the following steps:first,hollow polymer spheres with large hollow interior were prepared using sodium oleate as the hollow core generator,and 2,4-dihydroxybenzoic acid and hexamethylene tetramine(HMT) as the polymer precursors under hydrothermal conditions;Fe 3+ or Ag + cations were then introduced into the as-prepared hollow polymer spheres through the carboxyl groups;finally,the hollow polymer spheres can be pseudomorphically converted to hollow carbon spheres during pyrolysis process,meanwhile iron or silver nanoparticles can also be formed in the carbon shell simultaneously.The structures of the obtained functional hollow carbon spheres were characterized by TEM,XRD,and TG.As an example,Ag-doped hollow carbon spheres were used as colloid catalysts which showed high catalytic activity in 4-nitrophenol reduction reaction.     

A general protocol to coat titania shell on carbon-based composite cores using carbon as coupling agent

We present herein a general protocol to coat titania shell on carbon-based composite cores via the hydrolysis of titanium tetrabutoxide in a mixed solvent with the catalysis of ammonia. As coupling agent, their carbonaceous component can adsorb counter-charged NH₄⁺, and then the negatively charged ≡TiO⁻ species are adsorbed via electrostatic interaction to form TiO₂ shell. Various carbon-based cores with different functional components, such as Ag/C core/shell spheres, Ag/C nanocables, as well as magnetic (C-Fe₃O₄) hollow spheres can be coated with titania shell to form corresponding core/shell composites. Their optical or magnetic property is also investigated. Finally, anatase-phase titania shell with rough surface can be generated via hydrothermal treatment of aforementioned titania coated composites, which can further introduce the properties of anatase-phase titania to the composites.     

可移动金核的二氧化钛空心球合成及光催化性质

Uniform hollow Au@TiO₂ core shell spheres with moveable Au nanoparticles were synthesized based on templating against Au@carbon spheres. The diameter of the shell of the Au@TiO₂ spheres could be controlled by adjusting the Ti(OC₄H₉)₄ hydrolyzing reaction time or the ratio of Ti(OC₄H₉)₄ to Au@carbon spheres, and the shell thickness of the core-shell spheres can be varied from 25 nm to 40 nm. As prepared hollow Au@TiO₂ core-shell spheres display enhanced photocatalytic activity in the initial stage of photocatalytic degradation of methylene blue compared with pure hollow TiO₂ spheres and the commercial photocatalyst TiO₂(P-25).     

Preparation of Porous Hollow SiO2 Spheres by a Modified St?ber Process Using MF Microspheres as Templates

Using the surface charged and acid dissolvable melamine formaldehyde (MF) microspheres as sacrificial hard templates, silica coated MF core?Cshell composite microspheres, denoted as MF@SiO₂, were synthesized via a surfactant-assisted sol?Cgel process by using tetraethyl orthosilicate (TEOS) as silica source. Hollow SiO₂ spheres with mesoporous shells were then obtained after selective removal of the MF cores and the pore directing surfactant by hydrochloric acid etching or calcinations in air. Interesting shrinkage phenomena were observed in both the hollow products derived from hydrochloric acid etching and calcinations. The influence of the ratio of MF sphere to TEOS and the removal method of the MF core on the size of the hollow spheres, the shell thickness and the shell surface roughness have been studied. The composition, the thermal stability, the morphology, the surface area and pore size distribution, the wall thickness and adsorption properties of the hollow spheres derived from hydrochloric acid etching and calcinations were also investigated and compared based on the FTIR, SEM, TEM, TGA, Nitrogen adsorption?Cdesorption and spectrophotometer techniques or measurements.     

Synthesis of Hollow Mesoporous TiO2 Microspheres with Single and Double Au Nanoparticle Layers for Enhanced Visible‐Light Photocatalysis

A facile method was used to prepare hollow mesoporous TiO₂ and Au@TiO₂ spheres using polystyrene (PS) templates. Au nanoparticles (NPs) were simultaneously synthesized and attached on the surface of PS spheres by reducing AuCl₄^? ions using sodium citrate which resulted in the uniform deposition of Au NPs. The outer coating of titania via sol‐gel produced PS@Au@TiO₂ core–shell spheres. Removing the templates from these core–shell spheres through calcination produced hollow mesoporous and crystalline Au@TiO₂ spheres with Au NPs inside the TiO₂ shell in a single step. Anatase spheres with double Au NPs layers, one inside and another outside of TiO₂ shell, were also prepared. Different characterization techniques indicated the hollow mesoporous and crystalline morphology of the prepared spheres with Au NPs. Hollow anatase spheres with Au NPs indicated enhanced harvesting of visible light and therefore demonstrated efficient catalytic activity toward the degradation of organic dyes under the irradiation of visible light as compared to bare TiO₂ spheres.     

Multishelled Metal Oxide Hollow Spheres: Easy Synthesis and Formation Mechanism

Uniform multishelled NiO, Co₃O₄, ZnO, and Au@NiO hollow spheres were synthesized (NiO and Co₃O₄ hollow spheres for the first time) by a simple shell‐by‐shell self‐assembly allowing for tuning of the the size, thickness and shell numbers by controlling the heat treatment, glucose/metal salt molar ratio, and hydrothermal reaction time. These findings further the development of synthetic methodologies for multishelled hollow structures and could open up new opportunities for deeper understanding of the mechanisms of shell‐by‐shell self‐assembly. Moreover, the double‐shelled NiO hollow sphere exhibits a higher photocatalytic activity for degradation of methyl orange than its morphological counterparts.     

混晶海胆状TiO2空心球多级结构的制备及其对亚甲基蓝的光催化降解

用简单的无模板水热法可控合成了金红石相锥刺和锐钛矿相空心球的海胆状TiO2多级结构。研究了制备介质pH值和反应时间对形貌的影响。空心球上锥刺的密度可以通过改变反应条件加以调控。对海胆状TiO2多级结构可能的形成机理进行了研究。将不同锥刺密度的TiO2空心球应用于亚甲基蓝降解的光催化研究,结果表明低锥刺密度的TiO2空心球的光催化效果优于P25-TiO2,更优于锥刺多和无锥刺的光滑TiO2空心球。     

Novel sol–gel synthesis of N-doped TiO<Subscript>2</Subscript> hollow spheres with high photocatalytic activity under visible light

Novel ammonia and triethanolamine assisted sol–gel synthesis method was developed to fabricate the N-doped TiO₂ hollow spheres. The prepared hollow spheres were in submicron size and had good morphology and high specific surface area. Polystyrene (PS) latexes in size of 470 nm were used as the templates to fabricate PS/TiO₂ core–shell spheres. Here ammonia and triethanolamine was first employed together to control the sol–gel process. The N-doped TiO₂ hollow spheres were got after calcinations of the core–shell spheres by using triethanolamine as N source, and the amount of doped N could be easily adjusted by changing the amount of triethanolamine. The hollow spheres had distinct visible light response, and the optical response shifted more to the visible region as the amount of doped N increases. The photodegradation of methylene blue expressed the high photocatalytic activity of the N-doped TiO₂ hollow spheres under visible light.     

Formation of Triple‐Shelled Molybdenum–Polydopamine Hollow Spheres and Their Conversion into MoO2/Carbon Composite Hollow Spheres for Lithium‐Ion Batteries

Unique triple‐shelled Mo‐polydopamine (Mo‐PDA) hollow spheres are synthesized through a facile solvothermal process. A sequential self‐templating mechanism for the multi‐shell formation is proposed, and the number of shells can be adjusted by tuning the size of the Mo‐glycerate templates. These triple‐shelled Mo‐PDA hollow spheres can be converted to triple‐shelled MoO₂/carbon composite hollow spheres by thermal treatment. Owing to the unique multi‐shells and hollow interior, the as‐prepared MoO₂/carbon composite hollow spheres exhibit appealing performance as an anode material for lithium‐ion batteries, delivering a high capacity of ca. 580 mAh g^?1 at 0.5 A g^?1 with good rate capability and long cycle life.     

Template free fabrication of hollow hematite spheres via a one-pot polyoxometalate-assisted hydrolysis process

Uniform hollow hematite (α-Fe₂O₃) spheres with diameter of about 600-700 nm and shell thickness lower than 100 nm are obtained by direct hydrothermal treatment of dilute FeCl₃ and tungstophosphoric acid H₃PW₁₂O₄₀ solution at 180 °C. The hollow spheres are composed of robust shells with small nanoparticles standing out of the surface and present a high-surface area and a weak ferromagnetic behavior at room temperature. The effect of concentration of H₃PW₁₂O₄₀, reaction time and temperature for the formation of the hollow spheres are investigated in series of experiments. The formation of the hollow spheres may be ascribed to a polyoxometalte-assisted forced hydrolysis and dissolution process.     

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.     

Template synthesis of hydrogel composite hollow spheres against polymeric hollow latex

Hierarchically structured hydrogel hollow spheres with functional hydrogels located at desired sites are expected to have new properties. We have developed a facile swelling polymerization route using a polymer hollow sphere as template to synthesize hierarchically structured hydrogel hollow spheres. It is significant to pre-swell the template shell with good solvents, such as chloroform containing oil-soluble initiators to control interaction, thus, polymerization locus of different water-soluble functional monomers. Some representative hydrogel composite hollow spheres such as poly(N-isopropylarylamide) and poly(acrylic acid) with different morphologies have been synthesized. Hydrogels with functional groups can favorably complex with desired materials; hierarchically structured inorganic or polymer composite hollow spheres are synthesized by a sol–gel process of the inorganic precursor by using different hydrogel composite hollow spheres as templates.     

Highly ordered three dimensional macroporous carbon spheres and their acid catalytic properties

Highly ordered three dimensional macroporous carbon spheres bearing sulfonic acid groups (MPCS-SO₃H) were prepared by incomplete carbonization of glucose in silica crystal bead template, followed by sulfonation and removal of the template. The composition and porous structure of the obtained carbon spheres were investigated by physical adsorption of nitrogen, scanning electron microscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy techniques. While the Fourier-transform infrared spectroscopy was used to characterize the functional groups on the surface of carbon spheres. The catalytic properties of the MPCS-SO₃H were evaluated by esterification of ethanol with acetic acid, indicating that MPCS-SO₃H possess remarkable catalytic performance (high stability and acid catalytic ability) for the esterification.     

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.     

Fabrication of hollow titania microspheres with tailored shell thickness

Submicron hollow spheres are an interesting class of materials that receive significant attention nowadays. Closed and mechanically robust homogeneous hollow titania microspheres with as much shell thickness as 130 nm were fabricated by coating polystyrene beads with titania nanoparticles using sol–gel chemistry and subsequently removing the core either via heating or a chemical dissolution process. The thickness of the titania shell deposited on polystyrene core was finely tuned between 100 and 130 nm by varying the concentration of titania precursor, i.e., Ti(OEt)₄ salt from 0.5 to 2 mM during the coating process. The obtained hybrid core–shell particles and hollow microspheres were characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray diffraction, and thermo-gravimetric analysis. The approach employed is well suited to the preparation of titania-coated polystyrene hybrid particles and hollow titania spheres, which can find their applications as novel building blocks with unique optical properties for fabrication of advanced materials, catalyst, and drug delivery system.     

Preparation of novel porous carbon spheres from corn starch

Irregular porous carbon spheres were successfully prepared from Na₂SnO₃ coated corn porous starch by carbonization. The product was characterized with X-ray diffraction and scanning electron microscope (SEM). It is verified that the irregular porous carbon spheres are composed of disordered carbon, and the skeleton and pores of the corn porous starch was well preserved after carbonization. The pore size of the irregular porous carbon spheres is almost the same, which is similar to that of the porous starch. And the pore size decreases from about 0.91 μm to 0.53 μm measured from the SEM pictures. The texture of the irregular porous carbon spheres is mainly determined by that of porous starch.     

A scanning electron microscopy study on hollow silica microspheres: defects and influences of the synthesis composition

Defects on hollow silica spheres synthesized in a tetraethylorthosilicate-octylamine-HCl-H₂O system were recorded by scanning microscope. Based on the results, influences of synthesis composition on the formation of these defects are discussed. It is evidenced that products prepared with different octylamine-to-tetraethylorthosilicate ratios may have surface depressions, cracks and non-hollow microspheres. However, by changing water and acid additions, these defects could be reduced or eliminated. Generally, samples synthesized with a large octylamine addition commonly exhibit surface depressions. A small octylamine or a large water addition benefits the formation of solid silica microspheres among the product. Acid, although is not indispensable for the formation of hollow spheres, helps to eliminate or reduce depressions on the hollow shells. It is explained that the added acid gives rise to a relative localized fast hydrolysis versus condensation, facilitating an easy mobility of hydrolyzed silica species, and consequently the shell surface is smoothened.     

Hematite nanoparticles as polystyrene microsphere coatings and hollow spheres: preparation and characterization

A novel method of fabricating composite particles with core–shell structures is demonstrated. The particles comprised monodisperse submicrometer-sized copolymer latex spheres as cores and Fe₂O₃ crystallites as shells. The shell was formed by controlled hydrolysis of aqueous iron solutions, and the growth of hematite on the surface of the copolymer spheres was controlled by slow injection. Hollow spheres were obtained by calcinations of the so-coated copolymer lattices at 500°C in air. The void size of these hollow spheres was determined by the diameter of the copolymer template, and the wall thickness could be easily controlled in the range of 20–60 nm by using this coating process. The structure and the composition of the spheres were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). It can be seen that a crystallite change and a crystal phase transformation occurred during coating and calcination of the composite spheres. The formation of the composite particles is simply explained by the nucleation of iron oxide on the surface of the latex followed by growth of the iron compound shell.     

Synthesis and Photoluminescence Properties of Uniform Y2O3:Eu3+ Hollow Spheres with Tunable Shell Thickness

Y2O3:Eu3+ hollow spheres were successfully prepared with melamine formaldehyde(MF) spheres as template. The MF spheres played a significant role in directing the formation of the hollow shells which are composed of numerous primary nanoparticles. Furthermore, the shell thickness of these hollow spheres could be readily tailored by adjusting the dosage of MF template. Based on the photoluminescence(PL) investigation, the red emission intensities(613 nm) of these Y2O3:Eu3+ hollow spheres are greatly influenced by their shell thickness and it was found that hollow spheres with thin shell thickness and intact hollow structures permit a better PL performance.     

Selective Functionalization of Hollow Nanospheres with Acid and Base Groups for Cascade Reactions

The inner‐surface functionalization of hollow silica spheres has rarely been reported and is still a challenging topic. Herein, we report a deacetalization–Henry cascade reaction catalyzed by dual‐functionalized mesoporous silica hollow nanospheres with basic amine groups (?NH₂) on the internal shell and carboxylic acid groups (?COOH) on the external shell. The selective functionalization has been realized by a combination of “step‐by‐step post‐grafting” and “cationic surfactant‐assisted selective etching” strategy. Compared to unisolated catalyst, the selectively isolated acidic and basic dual catalyst provides excellent catalytic performance for the deacetalization–Henry cascade reaction in terms of both activity (>99 %) and selectivity (95 %).