A facile synthesis of bimodal mesoporous silica and its replication for bimodal mesoporous carbon

Bimodal mesoporous silica material composed of 30-40 nm sized nanoparticles with 3.5 nm sized three-dimensionally interconnected mesopores was synthesized under neutral conditions using sodium silicate as a silica source. Using the bimodal mesoporous silica as a template, bimodal mesoporous carbon having 4 nm sized framework mesopores and approximately 30 nm sized textural pores was synthesized.     

Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor

Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.     

Gas diffusion and microstructural properties of ordered mesoporous silica fibers

Pore and surface diffusion of carbon dioxide (CO(2)) and ethylene (C(2)H(4)) in the nanopores of ordered mesoporous silica fibers about 200 microm in length was measured by the transient gravimetric method. The experimentally determined pore diffusivity data, coupled with the porosity, pore size, and fiber length, are used to obtain the actual length of the nanopores in silica fibers. These measurements reveal a structure of the ordered nanopores whirling helically around the fiber axis with a spiral diameter of about 15 microm and a pitch value of 1.6 microm. At room temperature the surface diffusion contributes about 10% to the total diffusional flux for these two gases in the nanopores of the ordered mesoporous silica fibers. The surface diffusion coefficients for the ordered mesoporous silica fibers are about 1 order of magnitude larger than the non-ordered mesoporous alumina or silica with similar pore size.     

Electrochemical study of o-toluidine blue impregnated in mesoporous silica channels

This paper reports an electrochemical study of ordered mesoporous silica impregnated with a cationic dye (o-toluidine blue), prepared with a non-ionic surfactant as the structure-directing agent. O-toluidine blue was chosen because of its utility as an electron transfer mediator (redox catalyst). O-toluidine blue impregnated mesoporous silica was characterized by nitrogen sorption porosimetry, small angle X-ray scattering, infrared spectroscopy, scanning electron microscopy and cyclic voltammetry using chemically modified carbon paste electrodes. Results indicate that the dye is located within the ordered mesopores of micron-sized silica spheres.     

General synthesis of mesoporous spheres of metal oxides and phosphates

Monodisperse and high-surface-area mesoporous inorganic spheres of various compositions including metal oxides, mixed oxides, and metal phosphates are prepared by templating mesoporous carbon spheres which are replicated from spherical mesoporous silica. Due to the rigid and thermally stable framework of carbon template, the crystalline phases of the obtained metal oxide spheres can be readily tailored by controlling crystalline temperatures. Moreover, the sphere morphologies can be changed from solid structure to hollow structure in some cases by changing the polarity of the precursor, due to the hydrophobic nature of carbon template.     

Synthesis of carbon tubes with mesoporous wall structure using designed silica tubes as templates

Hollow silica tubes with mesoporous wall structure were synthesized through the sol-gel reactions of tetraethoxysilane and n-octadecyltrimethoxysilane (TEOS/C18-TMS) on the surface of ammonium dl-tartrate crystals. Novel hollow carbon tubes with mesoporous walls and rectangular-shaped channels were fabricated using the silica tubes as templates.     

Synthesis of ordered mesoporous carbon monoliths with bicontinuous cubic pore structure of Ia3d symmetry

Large-diameter-sized mesoporous carbon monoliths with bicontinuous cubic structure of Ia3d symmetry have been synthesized by using mesoporous silica monoliths as hard templates; such carbon monoliths show potential application of advanced electrodes and electrochemical double layer capacitors.     

Selective chemical vapor deposition synthesis of double-wall carbon nanotubes on mesoporous silica

Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes.     

Encapsulation of enzyme in large mesoporous material with small mesoporous windows

Trypsin has been encapsulated in the mesopores of a hierarchical mesoporous silica material synthesized via Cu(I) catalyzed azide-alkyne click reaction between azide functionalized large spherical SBA-15 particles and alkyne functionalized mesoporous silica nanoparticles (MSNs). Encapsulated trypsin functions as an efficient biocatalyst and can be recycled several times.     

Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas

Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.     

Vesicle adsorption on mesoporous silica and titania

Lipid bilayer formation via vesicle fusion on mesoporous silica and mesoporous titania was investigated using quartz crystal microbalance with dissipation monitoring (QCM-D) and fluorescent recovery after photobleaching (FRAP). Results showed that lipid bilayers were formed on mesoporous silica and that intact vesicle adsorption was obtained on mesoporous titania. From the FRAP results, it could be concluded that the lipid bilayer was fluid; however, it had a smaller diffusivity constant compared to bilayers supported on a nonporous silica.     

Direct electrochemistry of glucose oxidase immobilized on a hexagonal mesoporous silica-MCM-41 matrix

The direct electrochemistry of glucose oxidase (GOD) immobilized on a hexagonal mesoporous silica modified glassy carbon electrode was investigated. The adsorbed GOD displayed a pair of redox peaks with a formal potential of -417 mV in 0.1 M pH 6.1 phosphate buffer solution (PBS). The response showed a diffusion-controlled electrode process with a two-electron transfer coupled with a two-proton transfer reaction process. GOD immobilized on a hexagonal mesoporous silica retained its bioactivity and stability. In addition, the immobilized GOD could electrocatalyze the oxidation of glucose to gluconlactone by taking ferrocene monocarboxylic acid (FMCA) as a mediator in N(2) saturated solutions, indicating that the electrode may have the potential application in biosensors to analyze glucose. The sensor could exclude the interference of commonly coexisted uric acid, p-acetaminophenol and ascorbic acid and diagnose diabetes very fast and sensitively. This work demonstrated that the mesoporous silica provided a novel matrix for protein immobilization and the construction of biosensors.     

Facile synthesis of a sulfonated carbon-silica-meso composite and mesoporous silica

In this study we report a novel and simple method for preparing a sulfonated carbon-silica-meso composite showing high acidity and porosity useful for transformation of bulky molecules, where glucose was used as a carbon source as well as a non-surfactant templating precursor and the resultant composite upon calcination yielded the mesoporous silica.     

Room-temperature metal-activator-free phosphorescence from mesoporous silica

Room-temperature phosphorescence has been observed and studied on metal-activator-free mesoporous silica. The mesoporous silica was prepared using a nonionic triblock copolymer as the mesostructure-directing agent. The as-calcined products have a well-ordered porous structure and exhibit strong phosphorescence under ultraviolet light excitation. The luminescence spectra are featured with several peaks in the visible region. The luminescence intensity is found to vary as a function of the calcination temperature and reach a maximum around 500-600 °C, but the peak positions remain nearly unchanged. The average luminescence lifetime is several hundred microseconds, and the luminescence can persist for seconds after the excitation is switched off. In addition, due to the moderate calcination temperature, phosphorescent mesoporous silica monoliths with controllable sizes and shapes have been fabricated. Such mesoporous silica materials, including both powders and monoliths, with strong phosphorescence could find promising applications as low-density and eco-friendly phosphors and optically detectable drug carriers.     

Fabrication of mesoporous metal chalcogenide nanoflake silica thin films and spongy mesoporous CdS and CdSe

Mesoporous silica metal oxide (ZnO and CdO) thin films have been used as metal ion precursors to produce the first examples of mesoporous silica metal sulfide (meso-SiO(2) @ZnS, meso-SiO(2) @CdS) or silica metal selenide (meso-SiO(2) @ZnSe, meso-SiO(2) @CdSe) thin films, in which the pore walls are made up of silica and metal sulfide or metal selenide nanoflakes, respectively. A gentle chemical etching with a dilute HF solution of the meso-SiO(2) @CdS (or meso-SiO(2) @CdSe) produces mesoporous cadmium sulfide (meso-CdS) (or cadmium selenide, meso-CdSe). Surface modified meso-CdS displays bright blue photoluminescence upon excitation with a UV light. The mesoporous silica metal oxides are formed as metal oxide nanoislands over the silica walls through a self-assembly process of a mixture of metal nitrate salt-two surfactants-silica source followed by calcination step. The reactions, between the H(2) S (or H(2) Se) gas and solid precursors, have been carried out at room temperature and monitored using spectroscopy and microscopy techniques. It has been found that these reactions are: 1)?taking place through the diffusion of sulfur or selenium species from the top metal oxide layer to the silica metal oxide interface and 2)?slow and can be stopped at any stage to obtain mesoporous silica metal oxide metal sulfide or silica metal oxide metal selenide intermediate thin films.     

Synthesis of mesoporous silica helical fibers using a catanionic-neutral ternary surfactant in a highly dilute silica solution: biomimetic silicification

Mesoporous silica helical fibers in many different shapes have been synthesized in a highly dilute silicate solution at pH approximately 2.0 by using CnTMAB-SDS-P123 (n = 14-18) ternary surfactant as a template. The mesoporous silica helical fibers possess a well-ordered hexagonal mesostructure, high surface area, and large pore volume. Thus, the microtome sections of the helical fibers demonstrate a concentric mesotructure or two hemiconcentric mesostructures. In addition to triblock copolymer, adding the proper amount of 1-butanol or pentanol can promote the yield of the helical fibers as well. The yield of the surfactant-templated helical fibers is also dependent on the water content, reaction temperature, and pH value of the solution. The mesoporous silica helical fiber can be used as a solid template to prepare mesoporous carbon helical fibers via impregnation of phenol-formaldehyde, pyrolysis, and silica removal.     

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.     

Synthesis of mesoporous silica nanobamboo with highly dispersed tungsten carbide nanoparticles

By controlling the interaction between cationic surfactant micelles and ammonium metatungstate during the formation of mesoporous silica structure, highly dispersed tungsten carbide (WC) nanoparticles of 2.0 nm in diameter on mesoporous silica nanospheres were synthesized at lower concentration of ammonium metatungstate. With additional ammonium metatungstate, a novel mesoporous silica nanobamboo structure was formed with bimodal size-distributed WC nanoparticles, in which 2.0 nm WC was homogeneously distributed in nanobamboo's mesoporous silica wall and those with larger diameter (10.0-20.0 nm) were only formed on the nanobamboo's inner surface and at its internodes. The mesoporous silica nanobamboo also had a very high tensile strength due to its bamboo-like structure.     

Microstructure and photoluminescence of Ge-doped mesoporous silica

Nanostructured Ge-doped mesoporous silica powder and thin film were prepared with a cetyltrimethylammonium bromide self-assembled template to investigate the doping effects on the structure and optical properties of mesoporous silica. The X-ray diffraction, transmission electron microscopy and photoluminescence (PL) results suggest that the Ge-doped mesoporous silica with Ge/Si molar ratio of 0.01 was characterized by the strongest PL intensity without phase separation. Worm-like Ge-doped porous silica with specific area up to 987 m²/g could be obtained in this study, in which some Si atoms were replaced by Ge atoms according to the X-ray photoelectron spectroscopy analyses. The PL intensity of mesoporous silica could be increased by germanium-induced oxygen-related defects, but for the samples with Ge/Si molar ratios larger than 0.01, the PL intensity decreased due to the phase separation of germanium oxide.     

Structure and infrared emissivity of polyimide/mesoporous silica composite films

Polyimide/mesoporous silica composite films were prepared by direct mixing of polyamic acid solution and silylated mesoporous silica particles, or by condensation polymerization of dianhydride and diamine with silylated mesoporous silica particles in N,N-dimethylacetamide, followed with thermal imidization. Structure and glass transition temperatures of the composite films were measured with FTIR, SEM, EDX, XPS and DMTA. The results show that the silylated mesoporous silica particles in the composites tend to form the aggregation with a strip shape due to phase separation. The composite films exhibit higher glass transition temperature as comparing with that of pure polyimide. It is found that the composite films present lower infrared emissivity value than the pure polyimide and the magnitude of infrared emissivity value is related to the content of silylated mesoporous silica in the composite films. Inhibiting actions of silylated mesoporous silica on infrared emission of the composite films may be owing to presence of nanometer-scale pores in silylated mesoporous silica.