Elongated silica nanoparticles with a mesh phase mesopore structure by fluorosurfactant templating

Mesoporous silica materials with pore structures such as 2D hexagonal close packed, bicontinuous cubic, lamellar, sponge, wormhole-like, and rectangular have been made by using surfactant templating sol-gel processes. However, there are still some "intermediate" phases, in particular mesh phases, that are formed by surfactants but which have not been made into analogous silica pore structures. Here, we describe the one-step synthesis of mesoporous silica with a mesh phase pore structure. The cationic fluorinated surfactant 1,1,2,2-tetrahydroperfluorodecylpyridinium chloride (HFDePC) is used as the template. Like many fluorinated surfactants, HFDePC forms intermediate phases in water (including a mesh phase) over a wider range of compositions than do hydrocarbon surfactants. The materials produced by this technique are novel elongated particles in which the layers of the mesh phase are oriented orthogonal to the main axis of the particles.     

Templating mesoporous silica with chiral block copolymers and its application for enantioselective separation

In this paper we describe the synthesis of chiral mesoporous silica based on chiral block copolymers of poly(ethylene oxide) and of d-phenylalanine (PEO-b-D-Phe) as a surfactant template. The resulting porous structures are characterized by nitrogen sorption experiments, transmission electron microscopy, and small-angle XRD. It is shown that chiral block copolymers of PEO-b-D-Phe are effective as a surfactant template for the preparation of silica materials with highly ordered periodic mesoporous structures of hexagonal symmetry with a pore size of ca. 5 nm and high surface areas of ca. 700 m2/g. The enantioselectivity feature of this porous silica, after the extraction of the chiral copolymers, was examined by selective adsorption of enantiomers and racemic solutions of valine. The selective adsorption was measured by circular dichroism (CD) spectroscopy. A chiral selectivity factor of 2.34 was found with the D enantiomer of valine adsorbed preferably.     

Porous Silica Particles Prepared from Silicon Tetrachloride Using Ultrasonic Spray Method

Silica particles having the median diameter of 1 to 3 μm were prepared from silicon tetrachloride vapor by a reaction with water droplets using the ultrasonic spray method. The particle sizes of silicas were controlled by changing the composition of silicon tetrachloride and water. These silica particles had microporous structures from nitrogen and water adsorption measurements. The microporous and mesoporous particles were prepared from the reaction of water droplets including sodium and potassium carbonates with silicon tetrachloride vapor. Copyright 1999 Academic Press.     

Understanding on the Surfactants Engineered Morphology Evolution of Block Copolymer Particles and Their Precise Mesoporous Silica Replicas

Surfactant-directed block copolymer(BCP) particles have gained intensive attention owing to their attractive morphologies and ordered domains. However, their controllable fabrication suffers several limitations including complex design and synthesis of multiple surfactant systems, limited choices of block copolymers, and time-consuming post-processes, etc. Herein, a surfactant size-dependent phase separation route is proposed to precisely manipulate the architectures of the anionic block copolymer particles in the binary co-assembly system of BCP and surfactants. In the system of polystyrene block polyacrylic acid (PS-b-PAA) and quaternary ammonium surfactants, it is verified that facile control on the ordered phase separation structures and morphologies of BCP particles can be achieved via simply varying the alkyl lengths of the surfactants. The cationic surfactants are demonstrated participating in the fabrication of the internal structures of BCP particles. Especially, it is found that the cationic surfactants are integrate into the anionic polyacrylic acid(PAA) domain of BCP particles of PS-b-PAA to influence the volume fraction of PAA blocks, so that varied architectures of BCP particles are constructed. Based on these understandings, spherical or ellipsoidal BCP particles are obtained as expected, as well as their precisely inorganic mesoporous silica replicas through the block copolymer nanoparticle replicating route. More interestingly, the ellipsoidal mesoporous silica exhibits higher cellular internalization capability due to its lower energy expenditure during the internalization process, which presents promising potentials in biomedical applications, especially for high-efficient drug delivery systems. These findings may provide valuable insights into the confinement assembly of anionic block copolymers and the creation of special nanocarriers for high-efficiency biomacromolecule delivery in the biomedical community.     

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.     

Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO₂:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.     

Synthesis and formation of hierarchical mesoporous silica network in acidic aqueous solutions of sodium silicate and cationic surfactant

Synthesis and formation of hierarchical mesoporous silica network in acidic aqueous solutions of commercial sodium silicate and cationic surfactant were studied by SEM, TEM, XRD and nitrogen adsorption-desorption methods. The formation process occurs through several steps, involving (1) formation of mesoporous silica nanoparticles; (2) aggregation of mesoporous silica nanoparticles into blocks; (3) growth of silica nanorods in closely-packed arrays by merging of silica nanoparticles; (4) separation of the nanorods to form 3D silica network; and (4) shrinking of the mesoporous silica network. The as-prepared 3D silica network exhibits bimodal morphology constituting mesoporous and macroporous phases.     

Morphological and structural evolution of mesoporous silicas in a mild buffer solution and lysozyme adsorption

Mesoporous silicas with various morphologies and structures were synthesized with the aid of 2,2,4-trimethylpentane (TMP) in the presence of nonionic surfactant P123 [(EO)20(PO)70(EO)20] as a structure-directing agent under mild reaction conditions (HAc-NaAc buffer solution, pH 4.4). The ropelike particles formed by end-to-end interconnected nanorods were obtained at a TMP/P123 weight ratio of 0.5. It is noteworthy to mention that the mesoporous nanorods have channels running parallel to the short axis. The silica hollow spheres can be obtained at a higher TMP/P123 weight ratio because of the fusion of the primary nanorods around the interface of the O/W emulsion. Initial synthesis temperatures of 15, 25, and 40 degrees C can lead to mesoporous silicas with highly ordered 2D hexagonal mesostructure, vesicular mesostructure, and mesostructured cellular foams (MCF), respectively. The mesoporous silicas exhibit high adsorption capacity (up to 536 mg g(-1)) and very rapid (<5 min to reach equilibrium) lysozyme immobilization. More importantly, it is revealed that mesoporous silica hollow spheres with rugged surfaces can greatly accelerate the adsorption rate of the enzyme during the adsorption process.     

Preparation of mesoporous submicrometer silica capsules via an interfacial sol-gel process in inverse miniemulsion

Mesoporous silica capsules with submicrometer sizes were successfully prepared via the interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) in inverse miniemulsion by using hydrophilic liquid droplets as template. The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via sonication by using poly(ethylene-co-butylene)-b-poly(ethylene oxide) (P(E/B)-PEO) or SPAN 80 as surfactant. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed by the deposition of silica on the surface of droplets. The formation of capsule morphology was confirmed by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The mesoporous structure was verified by nitrogen sorption measurements. The specific surface area could be tuned by the variation of the amount of cetyltrimethylammonium bromide (CTAB) and TEOS, and the pore size by the amount of CTAB. The influences of synthetic parameters on the particle size and morphology were investigated in terms of the amount of CTAB, pH value in the droplets, TEOS amount, surfactant amount, and type of solvent with low polarity. A formation mechanism of silica capsules was proposed.     

Unusual dependence of particle architecture on surfactant concentration in partially fluorinated decylpyridinium templated silica

A series of porous silica particles is prepared with different concentrations of the fluorinated cationic surfactant 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10)-heptadecafluorodecyl)pyridinium chloride (HFDePC) to trace the changes in pore structure and particle morphology as the surfactant concentration increases. At the lowest concentration studied (1.5 mmol/L), the product consists of small round particles with close-packed cylindrical mesopores. As the HFDePC concentration increases, macroporous voids are introduced to create multi-chambered hollow particles with mesoporous walls. With a still higher concentration of HFDePC the macropore volume decreases, and elongated, tactoid-like nanoparticles are formed with random mesh-phase pores oriented with silica layers perpendicular to the main axis of the particles. Further increasing the concentration of HFDePC eventually leads to the formation of round particles with disordered pores. These changes are consistent with increasing HFDePC concentration favoring increasingly oblate or disklike micelles. The process of forming the elongated particles with random mesh-phase structure is investigated by TEM of chilled and dried samples. The results indicate that the oriented tactoid-like structure forms spontaneously within 2 min by co-assembly of silica and HFDePC rather than by preferred growth perpendicular to the layers. The particle shape and layer orientation are consistent with what would be expected for a liquid-crystal particle with orientation-dependent surface tension. Finally, we compare samples prepared with a high HFDePC and with good or poor mixing. With inadequate mixing, a gel layer forms at the top of the sample which is composed of elongated mesoporous particles with a thick coating of microporous silica. The lower particulate phase contains small disordered particles similar to those obtained in a well-mixed sample. Presumably, the structure of the upper layer results from initial immiscibility of the precursor and slow diffusion of silicates out of the gel.     

High-temperature synthesis of stable ordered mesoporous silica materials by using fluorocarbon-hydrocarbon surfactant mixtures

Highly ordered hexagonal mesoporous silica materials (JLU-20) with uniform pore sizes have been successfully synthesized at high temperature (150-220 degrees C) by using fluorocarbon-hydrocarbon surfactant mixtures. The fluorocarbon-hydrocarbon surfactant mixtures combine the advantages of both stable fluorocarbon surfactants and ordered hydrocarbon surfactants, giving ordered and stable mixed micelles at high temperature (150-220 degrees C). Mesoporous JLU-20 shows extraordinary stability towards hydrothermal treatment (100 % steam at 800 degrees C for 2 h or boiling water for 80 h), thermal treatment (calcination at 1000 degrees C for 4 h), and toward mechanical treatment (compressed at 740 MPa). Transmission electron microscopy images of JLU-20 show well-ordered hexagonal arrays of mesopores with one-dimensional (1D) channels and further confirm that JLU-20 has a two-dimensional (2D) hexagonal (P6 mm) mesostructure. 29Si HR MAS NMR spectra of as-synthesized JLU-20 shows that JLU-20 is primarily made up of fully condensed Q4 silica units (delta=-112 ppm) with a small contribution from incompletely cross-linked Q3 (delta=-102 ppm) as deduced from the very high Q4/Q3 ratio of 6.5, indicating that the mesoporous walls of JLU-20 are fully condensed. Such unique structural features should be directly attributed to the high-temperature synthesis, which is responsible for the observed high thermal, hydrothermal, and mechanical stability of the mesoporous silica materials with well-ordered hexagonal symmetry. Furthermore, the concept of "high-temperature synthesis" is successfully extended to the preparation of three-dimensional (3D) cubic mesoporous silica materials by the assistance of a fluorocarbon surfactant as a co-template. The obtained material, designated JLU-21, has a well-ordered cubic Im3m mesostructure with fully condensed pore walls and shows unusually high hydrothermal stability, as compared with conventional cubic mesoporous silica materials such as SBA-16.     

Use of the ternary phase diagram of a mixed cationic/glucopyranoside surfactant system to predict mesostructured silica synthesis

Mixed surfactant systems have the potential to impart controlled combinations of functionality and pore structure to mesoporous metal oxides. Here, we combine a functional glucopyranoside surfactant with a cationic surfactant that readily forms liquid crystalline mesophases. The phase diagram for the ternary system CTAB/H(2)O/n-octyl-beta-D-glucopyranoside (C(8)G(1)) at 50 degrees C is measured using polarized optical microscopy. At this temperature, the binary C(8)G(1)/H(2)O system forms disordered micellar solutions up to 72 wt% C(8)G(1), and there is no hexagonal phase. With the addition of CTAB, we identify a large area of hexagonal phase, as well as cubic, lamellar and solid surfactant phases. The ternary phase diagram is used to predict the synthesis of thick mesoporous silica films via a direct liquid crystal templating technique. By changing the relative concentration of mixed surfactants as well as inorganic precursor species, surfactant/silica mesostructured thick films can be synthesized with variable glucopyranoside content, and with 2D hexagonal, cubic and lamellar structures. The domains over which different mesophases are prepared correspond well with those of the ternary phase diagram if the hydrophilic inorganic species is assumed to act as an equivalent volume of water.     

Facile synthesis of monodisperse microspheres and gigantic hollow shells of mesoporous silica in mixed water-ethanol solvents

Mesoporous silica materials with a variety of morphologies, such as monodisperse microspheres, gigantic hollow structures comprising a thin shell with a hole, and gigantic hollow structures consisting of an outer thin shell and an inner layer composed of many small spheres, have been readily synthesized in mixed water-ethanol solvents at room temperature using cetyltrimethylammonium bromide (CTAB) as the template. The obtained mesoporous silica generally shows a disordered mesostructure with typical average pore sizes ranging from 3.1 to 3.8 nm. The effects of the water-to-ethanol volume ratio (r), the volume content of tetraethyl orthosilicate TEOS (x), and the CTAB concentration in the solution on the final morphology of the mesoporous silica products have been investigated. The growth process of gigantic hollow shells of mesoporous silica through templating emulsion droplets of TEOS in mixed water-ethanol solution has been monitored directly with optical microscopy. Generally, the morphology of mesoporous silica can be regulated from microspheres through gigantic hollow structures composed of small spheres to gigantic hollow structures with a thin shell by increasing the water-to-ethanol volume ratio, increasing the TEOS volume content, or decreasing the CTAB concentration. A plausible mechanism for the morphological regulation of mesoporous silica by adjusting various experimental parameters has been put forward by considering the existing state of the unhydrolyzed and partially hydrolyzed TEOS in the synthesis system.     

纳米SiO2/十二烷基氨基丙酸钠协同稳定的pH响应性Pickering乳状液

用纳米SiO₂颗粒与微量氨基酸型两性表面活性剂十二烷基氨基丙酸钠作复合乳化剂, 以正癸烷为油相, 制备了pH响应性O/W型Pickering乳状液. 室温下该乳状液在pH≤4.0 时稳定, 在pH≥6.0时不稳定, 因此, 可以通过改变水相的pH值使乳状液在稳定和破乳之间多次循环. 在酸性水介质中, 氨基酸型两性表面活性剂分子呈阳离子状态, 可通过静电作用吸附到带负电荷的SiO₂颗粒表面, 产生原位疏水化作用, 使其转变为表面活性颗粒; 而在中性和碱性水介质中, 氨基酸型两性表面活性剂呈两性或阴离子状态, 不能产生原位疏水化作用, 因而导致乳状液破乳. 相关作用机理通过吸附量、 Zeta电位及接触角等实验数据得以论证. 该刺激-响应性Pickering乳状液在乳液聚合、 油品输送以及燃料生产等领域具有重要的应用价值.     

A Single‐Step Synthesis of Electroactive Mesoporous ProDOT‐Silica Structures

The single‐step preparation of highly ordered mesoporous silica hybrid nanocomposites with conjugated polymers was explored using a novel cationic 3,4‐propylenedioxythiophene (ProDOT) surfactant (PrS). The method does not require high‐temperature calcination or a washing procedure. The combination of self‐assembly of the silica surfactant and in situ polymerization of the ProDOT tail is responsible for creation of the mesoporosity with ultralarge pores, large pore volume, and electroactivity. As this novel material exhibits excellent textural parameters together with electrical conductivity, we believe that this could find potential applications in various fields. This novel concept of creating mesoporosity without a calcination process is a significant breakthrough in the field of mesoporous materials and the method can be further generalized as a rational preparation of various mesoporous hybrid materials having different structures and pore diameters.     

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.     

Combined emulsion and solvent evaporation (ESE) synthesis route to well-ordered mesoporous materials

Control over morphology and internal mesostructure of surfactant templated silicas remains a challenge, especially when considering scaling laboratory syntheses up to industrial volumes. Here we report a method combining emulsification with the evaporation-induced self-assembly (EISA) method for preparing spherical, mesoporous silica particles. This emulsion and solvent evaporation (ESE) method has several potential advantages over classic precipitation routes: it is easily scaled while providing superior control over stoichiometric homogeneity of templating surfactants and inorganic precursors, and particle sizes and distributions are determined by principles developed for manipulating droplet sizes within water-in-oil emulsions. To demonstrate the method, triblock copolymer P104 is used as a templating amphiphile, generating unusually well-ordered 2D hexagonal (P6mm) mesoporous silica, while particle sizes and morphologies were controlled by varying the type of emulsifier and the method for emulsification.     

Ordered micro/mesoporous composite prepared as thin films

A new synthesis method for preparation of thin films and powders consisting of zeolite beta nanocrystals embedded in ordered mesoporous silica matrix is described. The final structures possessing bimodal porosity, i.e., high degree of mesophase order and spatially defined microporous zeolite nanocrystals are obtained via simultaneous solvent evaporation of preformed silica/surfactant/ethanol/nanosized zeolite beta assemblies. The films were characterized with grazing-incident diffraction (GID), nitrogen sorption based on gravimetric measurements with quartz crystal microbalance (QCM) devices, and transmission electron microscopy (TEM). It is shown that the incorporation of beta nanocrystals in the mesoporous silica matrix and the mesophase order itself can be controlled through the variation of the fractional amounts of the zeolite nanoparticles and silica/surfactant solutions. The HR-TEM measurements showed that the nanosized Beta microporous crystals are separated and at the same time connected through an ordered mesostructured matrix.     

Production of porous silica microparticles by membrane emulsification

A method for the production of near-monodispersed spherical silica particles with controllable porosity based on the formation of uniform emulsion droplets using membrane emulsification is described. A hydrophobic metal membrane with a 15 μm pore size and 200 μm pore spacing was used to produce near-monodispersed droplets, with a mean size that could be controlled between 65 and 240 μm containing acidified sodium silicate solution (with 4 and 6 wt % SiO(2)) in kerosene. After drying and shrinking, the final silica particles had a mean size in the range between 30 and 70 μm. The coefficient of variation for both the droplets and the particles did not exceed 35%. The most uniform particles had a mean diameter of 40 μm and coefficient of variation of 17%. By altering the pH of the sodium silicate solution and aging the gel particles in water or acetone, the internal structure of the silica particles was successfully modified, and both micro- and mesoporous near-monodispersed spherical particles were produced with an average internal pore size between 1 and 6 nm and an average surface area between 360 and 750 m(2) g(-1). A material balance and particle size analysis provided identical values for the internal voidage of the particles, when compared to the voidage as determined by BET analysis.     

电解质诱导聚集初级粒子制备介孔SiO_2材料

在无模板剂的条件下,通过在Stber合成过程中引入外加电解质成功地制备了具有介孔结构的SiO2粒子.实验结果表明,通过电解质的加入可以诱导Stber过程中初级SiO2粒子的聚集,从而得到了具有介孔结构和较强表面吸附能力的SiO2粒子.