Spherical carbon capsules with hollow macroporous core and mesoporous shell structures as a highly efficient catalyst support in the direct methanol fuel cell

Carbon capsules with hollow core and mesoporous shell (HCMS) structures were used as a support material for Pt(50)-Ru(50) catalyst, and the catalytic performance of the HCMS supported catalyst in the direct methanol fuel cell was described; the HCMS carbon supported catalysts exhibited much higher specific activity for methanol oxidation than the commonly used E-TEK catalyst by about 80%, proving that the HCMS carbon capsules are an excellent support for electrode catalysts in DMFC.     

Fabrication of bimodal porous silicate with silicalite-1 core/mesoporous shell structures and synthesis of nonspherical carbon and silica nanocases with hollow core/mesoporous shell structures

In this work, an attempt has been made to modify the shape and nanostructure of core-shell materials, which have been usually generated on the basis of amorphous spherical cores. Novel core-shell silicate particles, each of which consists of a silicalite-1 zeolite crystal core and mesoporous shell (ZCMS), were synthesized for the first time. The ZCMS core-shell particles are unique because they are of pseudohexagonal prismatic shape and have hierarchical porosity of both a uniform microporous core and a mesoporous shell coexisting in a particle framework. The nonspherical bimodal porous core-shell particles were then utilized as templates to fabricate a new carbon replica structure. Interestingly, the pore replication process was carried out only through the mesopores in the shell, and not through the micropores due to the narrower micropore size in the core, resulting in nonspherical carbon nanocases with a hollow core and mesoporous shell (HCMS) structure. Nonspherical silica nanocases with HCMS structure were also generated by replication using the carbon nanocases as templates, which are not possible to synthesize through other synthetic methods. Interestingly, the pseudohexagonal prismatic shape of the zeolite crystals was transferred onto the carbon and silica nanocases.     

Dual latex/surfactant templating of hollow spherical silica particles with ordered mesoporous shells

Hollow spherical silica particles with hexagonally ordered mesoporous shells are synthesized with the dual use of cetyltrimethylammonium bromide (CTAB) and unmodified polystyrene latex microspheres as templates in concentrated aqueous ammonia. In most of the hollow mesoporous particles, cylindrical pores run parallel to the hollow core due to interactions of CTAB/silica aggregates with the latices. Effects on the product structure of the CTAB:latex ratio, the amount of aqueous ammonia, and the latex size are studied. Hollow particles with hexagonally patterned mesoporous shells are obtained at moderate CTAB:latex ratios. Too little CTAB causes silica shell growth without surfactant templating, and too much induces nucleation of new mesoporous silica particles without latex cores. The concentration of ammonia must be large to induce co-assembly of CTAB, silica, and latex into dispersed particles. The results are consistent with the formation of particles by addition of CTAB/silica aggregates to the surface of latex microspheres. When the size and number density of the latex microspheres are changed, the size of the hollow core and the shell thickness can be controlled. However, if the microspheres are too small (50 nm in this case), agglomerated particles with many hollow voids are obtained, most likely due to colloidal instability.     

Elaboration of monodisperse spherical hollow particles with ordered mesoporous silica shells via dual latex/surfactant templating: radial orientation of mesopore channels

Monodisperse spherical hollow nanoparticles of mesoporous silica featuring mesopores with a radial orientation in the silica shell were synthesized via a dual-templating method. Specifically designed polystyrene latexes with anionic or cationic surface charges acted as the core templates, while cetyltrimethylammonium bromide served as a co-template to structure the mesopore formation during tetraethoxysilane hydrolysis/condensation. The particles were well-separated and presented homogeneous mesoporous silica shells. Average particle diameters were less than 200 nm, and the particles displayed high values of specific surface area and pore volume. The shell thickness and the hollow core diameter could be tuned independently while the radial pore structure was preserved. A detailed analysis of the nitrogen adsorption-desorption isotherms proved that the central cavity was completely isolated from the external medium, that is, only accessible through the radial mesopores of the shell. Consequently, our particles gather the advantages of a well-defined structure, straight penetrating channels across the silica shell, and a high accessible porous volume of the central core. These properties make them far better candidates than simple mesoporous particles for any storage and/or controlled release applications.     

单分散中空介孔结构的盐模板合成及形貌调控

中空介孔结构因具有丰富的内部空间以及多孔渗透性外壳等优势,在催化、能源储存与转化及生物医药等领域得到了广泛应用.然而,目前仍然缺少高效、简便且绿色的合成中空介孔结构的方法.本文以柠檬酸钠胶体颗粒作为模板,通过十六烷基三甲基溴化氨(Cetyltrimethylammonium bromide, CTAB)胶束与正硅酸四乙酯(Tetraethyl orthosilicate, TEOS)的水解低聚物在胶体颗粒表面进行界面共组装,直接生长介孔二氧化硅壳层;然后通过简便的醇洗和水洗分别除去CTAB胶束和柠檬酸钠胶体颗粒后,得到中空介孔结构.进一步研究表明,负电荷的柠檬酸钠胶体颗粒与CTAB胶束之间的静电相互作用是诱导氧化硅低聚物在颗粒表面进行交联组装的关键.基于此,通过控制生长时间实现了对中空介孔结构形貌和壳层厚度的精确调控.所得中空介孔二氧化硅纳米球可以显著增强物质的扩散传输,是理想的催化剂载体,负载金纳米颗粒后可以高效催化4-硝基苯酚的还原反应.研究结果为中空介孔材料的绿色简便合成提供了思路.     

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.     

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.     

Stimuli-responsive hydrogel hollow capsules by material efficient and robust cross-linking-precipitation synthesis revisited

Monodisperse stimuli-responsive hydrogel capsules were synthesized in the 100-nm-diameter to 10-μm-diameter range from poly(4-vinylpyridine) (P4VP) and poly(ethyleneimine) (PEI) through a simple, efficient two-step cross-linking-precipitation template method under conditions of a good solvent. In this method, the core-shell particles were obtained by the deposition (heterocoagulation mechanism) of the cross-linked P4VP, PEI, or their mixtures on the surfaces of the template colloidal silica particles in nitromethane (for PEI) or a nitromethane-acetone mixture (for P4VP and P4VP-PEI mixtures) in the presence of cross-linker 1,4-diiodobutane. The cross-linked polymeric shell swollen in a good solvent stabilized the core-shell colloids. This mechanism provided the conditions for the synthesis of core-shell colloids in a submicrometer range of dimensions with an easily adjusted shell thickness (wall of the capsules) ranging from a few to hundreds of nanometers. The chemical composition of the shell was tuned by varying the ratio of co-cross-linked shell-forming polymers (P4VP and PEI). In the second step, the hollow capsules were obtained by etching the silica core in HF solutions. In this step, the colloidal stability of the hollow capsules was provided by ionized P4VP and PEI cross-linked shells. The hollow capsules demonstrate that the pH- and ionic-strength-triggered swelling and shrinking result in size-selective uptake and release properties. Cross-linked via quaternized functional groups, P4VP capsules undergo swelling and shrinking transitions at a physiologically relevant pH of around 6. The 200-nm-diameter hollow capsule with 25-nm-thick walls demonstrated a factor of 2 greater capacity to accommodate cargo molecules than the core-shell particles of the same dimensions because of an internal compartment and a combination of radial and a circumferential swelling modes in the capsules.     

Synthesis of Monodisperse Hollow Carbon Nanocapsules by Using Protective Silica Shells

Monodisperse hollow carbon nanocapsules (<200 nm) with mesoporous shells were synthesized by coating their outer shells with silica to prevent aggregation during their high‐temperature annealing. Monodispersed silica nanoparticles were used as starting materials and octadecyltrimethoxysilane (C18TMS) was used as a carbon source to create core–shell nanostructures. These core–shell nanoparticles were coated with silica on their outer shell to form a second shell layer. This outer silica shell prevented aggregation during calcination. The samples were characterized by TEM, SEM, dynamic light scattering (DLS), UV/Vis spectroscopy, and by using the Brunauer–Emmett–Teller (BET) method. The as‐synthesized hollow carbon nanoparticles exhibited a high surface area (1123 m² g^?1) and formed stable dispersions in water after the pegylation process. The drug‐loading and drug‐release properties of these hollow carbon nanocapsules were also investigated.     

Polyelectrolyte-surfactant complex as a template for the synthesis of zeolites with intracrystalline mesopores

Mesoporous zeolite silicalite-1 and Al-ZSM-5 with intracrystalline mesopores were synthesized with polyelectrolyte-surfactant complex as the template. Complex colloids were first formed by self-assembly of the anionic polymer poly(acrylic acid) (PAA) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) in basic solution. During the synthesis procedure, upon the addition of the silica source, microporous template (tetrapropylammonium hydroxide), and NaCl, these PAA/CTA complex colloids underwent dissociation and gave rise to the formation of hollow silica spheres with mesoporous shells templated by CTAB micelles and PAA domains as the core. Under hydrothermal treatment, the hollow silica spheres gradually merged together to form larger particles with the PAA domains embedded as the space occupant, which acted as a template for intracrystalline mesopores during the crystallization of the zeolite framework. Amphiphilic organosilane was used to enhance the connection between the PAA domain and the silica phase during the synthesis. After calcination, single crystal-like zeolite particles with intracrystalline mesopores of about 5-20 nm were obtained, as characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and N(2) adsorption measurements. With the addition of an aluminum source in the synthesis, mesoporous zeolite Al-ZSM-5 with intracrystalline mesopores was also synthesized, and enhanced catalytic property was observed with mesoporous Al-ZSM-5 in acetalization of cyclohexanone with methanol.     

Preparation of hollow titania and strontium titanate spheres using sol–gel derived silica gel particles as templates

A facile approach, based on polyelectrolyte-mediated electrostatic adsorption of a water-soluble titanium complex on colloidal templates and hydrothermal treatment, is presented for the formation of hollow titania (TiO₂) and strontium titanate (SrTiO₃) spheres. Monodispersed silica gel particles were prepared by the sol?Cgel method and adopted as core templates. Deposition of a water-soluble titanium complex, titanium (IV) bis(ammoniumlactato)dihydroxide (TALH), on the silica gel particles was carried out via the layer-by-layer assembly technique. Hollow spheres were successfully formed from the core?Cshell particles. The silica gel particles used as core templates dissolved during hydrothermal treatment because of the particles?? undeveloped siloxane network. In addition, the hydrothermal treatment induced crystallization of the hollow shells. Therefore, the hydrothermal treatment played two roles; removal of the silica templates and crystallization of the hollow shells. When deionized water was used, hollow TiO₂ spheres were obtained. Hollow SrTiO₃ spheres could also be formed when an aqueous solution of Sr(OH)₂ was used. The approach presented here could be exploited as a novel and sustainable approach for the fabrication of a range of different inorganic hollow spheres.     

A facile and controllable one-pot synthesis approach to amino-functionalized hollow silica nanoparticles with accessible ordered mesoporous shells

The development of a practical synthetic method to functionalize hollow mesoporous silica with organic groups is of current intere st for selective adsorption and ene rgy storage applications.Herein,a facile and controllable one-pot approach for the synthesis of monodisperse amino-functionalized hollow mesoporous silica nanoparticles is presented.A novel solid-to-hollow structural transformation procedure of the silica nanoparticles is presented.The structural transformation is easily designed,as obse rved through transmission electro n microscopy,by tailo ring the HCl and N-lauroylsarcosine sodium molar ratio and the water content in the sol-gel.Ordered and radially oriented in situ aminofunctionalized mesochannels were successfully introduced into the shells of the hollow silica nanoparticles.A formation mechanism for the hollow mesoporous silica materials is discussed.     

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.     

Smart synthesis of hollow core mesoporous shell carbons (HCMSC) as effective catalyst supports for methanol oxidation and oxygen reduction reactions

The present paper describes an easy and quick synthesis of hollow core mesoporous shell carbon (HCMSC) simply templated from unpretreated solid core mesoporous shell silica using a cheap precursor like sucrose. Physical characterizations showed uniform spherical carbon capsules with a hollow macroporous core of ca. 305- and 55-nm-thick mesoporous shell, forming a well-developed 3-D interconnected bimodal porosity. High specific surface area and large pore volume were also confirmed, suggesting the obtained HCMSC as a promising catalyst support. HCMSC-supported Pt (nominal 20 wt.%) with an average Pt particle size of 1.9 nm was synthesized by wet impregnation, and a signal of strong interaction between carbon support and platinum was confirmed by X-ray photoelectron spectroscopy. In cyclic voltammetry and linear sweep voltammetry tests, the Pt/HCMSC electrode showed significantly higher electrocatalytic activity for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) if compared with commercial Pt/Vulcan catalyst. The durability tests by cyclic voltammetry showed for the Pt/HCMSC a lower electrochemical active surface area loss than the commercial one in acidic solution. All the primary tests suggested that the Pt/HCMSC, due to its particular structure and the high dispersion of noble metal particles, is a promising catalyst for fuel cell applications, for MOR and ORR.     

Sustained release control via photo-cross-linking of polyelectrolyte layer-by-layer hollow capsules

We describe the formation and permeability of polyelectrolyte multilayer hollow-shell capsules by photo-cross-linking and controlled-release (fluorescence) studies. The hollow shells were prepared by alternate layer-by-layer (LbL) adsorption of photo-cross-linkable benzophenone modified poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) on polystyrene particles, followed by removing the core with tetrahydrofuran. Zeta potential measurements, fourier transform infrared spectroscopy, and transmission electron microscopy were used to verify the LbL process integrity. A model drug, rhodamine B (RB), was successfully loaded into the polyelectrolyte hollow capsules. The release kinetics of RB was investigated using fluorescence spectroscopy. The permeability of RB through the hollow shells was effectively controlled based on UV irradiation time. It was shown that the release of RB molecules can be controlled by the degree of cross-linking induced in the multilayer.     

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     

Electrochemical Characteristics of Discrete,Uniform, and Monodispersed Hollow Mesoporous Carbon Spheres in Double‐Layered Supercapacitors

Core–shell‐structured mesoporous silica spheres were prepared by using n‐octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core–shell‐structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double‐layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer–Emmett–Teller (BET) area and larger pore size.     

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。     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.     

Novel drug delivery system of hollow mesoporous silica nanocapsules with thin shells: preparation and fluorescein isothiocyanate (FITC) release kinetics

Core-shell nanoparticles of Au@silica with a diameter of approximate 45–60 nm and wall thickness in range of 3–10 nm were synthesized by using 40 and 50 nm gold nanoparticles as the templates. The mesoporous particles are regulated by 3-aminopropyltrimethoxysilane addition. Hollow mesoporous silica nanocapsules (HMSNs) were prepared by using sodium cyanide to dissolve the gold cores. The characterization of Au@silica and HMSNs by transmission electronic microscope indicated that the silica shells were uniform and smooth, and also the porosity was proved by fluorescein isothiocyanate (FITC) release experiments. The ratio of hollow core to HMSNs is more than 70%. HMSNs were subsequently used as drug carrier to investigate FITC (as a model drug) release behaviors in vitro. Fluorescent spectrometry was performed to determine the release kinetics from the HMSNs. The release profiles are significantly different as compared with the control (free FITC), which show that HMSNs are good drug carriers to control drug release, and have high potential in therapeutic drugs delivery in future applications.