A novel anionic surfactant templating route for synthesizing mesoporous silica with unique structure

Anionic surfactants are used in greater volume than any other surfactants because of their highly potent detergency and low cost of manufacture. However, they have not been used as templates for synthesizing mesoporous silica. Here we show a templating route for preparing mesoporous silicas based on self-assembly of anionic surfactants and inorganic precursors. We use aminosilane or quaternized aminosilane as co-structure-directing agent (CSDA), which is different from previous pathways. The alkoxysilane site of CSDA is co-condensed with inorganic precursors; the ammonium site of CSDA, attached to silicon atoms incorporated into the wall, electrostatically interacts with the anionic surfactants to produce well-ordered anionic-surfactant-templated mesoporous silicas (AMS). These have new structures with periodic modulations as well as two-dimensional hexagonal and lamellar phases. The periodic modulations may be caused by the coexistence of micelles that differ in size or curvature, possibly owing to local chirality. These mesoporous silicas provide a new family of mesoporous materials as well as shedding light on the structural behaviour of anionic surfactants.     

Synthesis of amorphous supermicroporous zirconium phosphate materials by nonionic surfactant templating

Supermicroporous zirconium phosphate materials possessing wormhole-like pores in the size range 1.3-1.8 nm were synthesized by using nonionic poly(ethylene oxide) surfactant (e.g., C₁₆H₃₃(EO)₁₀, C₁₈H₃₅(EO)₁₀) as a structure directing agent. The textural and structural properties were characterized by powder X-ray diffraction, N₂ adsorption analysis, differential thermal analysis, scanning and transmission electron microscopy, ³¹P MAS NMR and infrared spectroscopy. The synthesized materials are amorphous, exhibiting high surface areas, narrow pore size distributions, excellent thermal stabilities (over 800 °C) and acidic properties. The supermicropore size of the synthesized zirconium phosphate may be tunable by the variation of alkyl chain length of the surfactant.     

Metallotropic liquid crystals formed by surfactant templating of molten metal halides

Liquid crystals consist of anisotropic molecular units, and most are organic molecules. Materials incorporating metals into anisotropic molecules, described as metallomesogens, have been prepared. Anisotropic structures such as one-dimensional chains and two-dimensional layers are frequently observed in solid-state inorganic materials, however, little is understood about structural organization in melts of such materials. Achieving liquid-crystalline behaviour in inorganic fluids should be possible if the anisotropic structure can be retained or designed into the molten phase. We demonstrated the ability to engineer zeolite-type structures into metal halide glasses and liquids. In this work we have engineered lamellar, cubic and hexagonal liquid-crystalline structure in metal-halide melts by controlling the volume fraction and nature of the inorganic block (up to 80 mol%) with respect to alkylammonium surfactants. The high metal content of these liquid-crystalline systems significantly advances the field of metallomesogens, which seeks to combine magnetic, electronic, optical, redox and catalytic properties common to inorganic materials with the fluid properties of liquid crystals.     

Carbon-supported growth of cross-linked platinum nanowires by surfactant templating and their elecrochemical characterization

Platinum/carbon (Pt/C) composite materials were prepared by the hydrazine reduction of H2PtCl6 confined to a mixed surfactant lytropic liquid crystal (LC)/C mixture with varying amounts of water. The reaction at relatively low water contents successfully yielded cross-linked Pt nanowires with wire-widths of 2-5 nm. The novel Pt nanostructure is believed to be from poorly hydrated hexagonal domains formed together with layered domains by the phase separation of the precursory LC mixture in the presence of carbon. Electrochemical measurements using cyclic volutammetry and membrane electrode assemblies revealed that the cross-linked nanowired Pt/C composite exhibits fairly high electrocatalytic activity for oxygen reduction reaction, as well as a high performance as the cathode material for polymer electrolyte fuel cells.     

Mesoporous hydroxyapatite by hard templating of silica and carbon foams for protein release

Calcium phosphates, particularly hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ (HA), are widely used for bone regeneration due to their biocompatibility and good resorption properties. However, their performance upon implantation is improved when they are associated with bioactive molecules such as growth factors. Using mesoporous HA leads to improved protein adsorption and release kinetics because the diameter of the mesopores (2–50 nm) is in the same range as their size. We prepared this type of material by the nanocasting method using three different templates: a silica foam and two carbon templates derived from it using propylene or sucrose as carbon source. We investigated the influence of the template, the calcination temperature and of the conditions during template removal. We obtained HA materials with a surface area of up to 90 m² g^?1 and with an intergranular mesopore volume of up to 0.4 cm³ g^?1. In this paper, we show for the first time that the synthesis of mesoporous HA from a mesoporous silica foam template allows eliminating the template at lower temperatures (in an alkaline medium), thus preventing the sintering of the HA. These materials have interesting properties for drug delivery applications. The protein adsorption and release capacities of these HAs were tested with two model proteins, bovine serum albumin (BSA), and Cytochrome C. These materials are an important milestone for future bone regeneration systems based on HA associated with human growth factor proteins.     

Controllable synthesis of silica hollow spheres by vesicle templating of silicone surfactants

Silica hollow spheres (SHSs) have been designed and prepared through three distinct synthetic routes based on the self-assembling of comb-like copolymer silicone surfactants. This process was based on the rule of similarities for hydrophobicity and hydrophilicity between the surfactant and a silica source. The directed silica wall formations were performed at different confined spaces of the vesicles, including the outer and inner surfaces, and the hydrophobic parts of the bi-layers. The resultant SHSs possess tailorable shell thicknesses (20–400 nm), particle sizes (200 nm–1.2 μm), and a high dispersibility in aqueous solutions.     

Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

Abstract

We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.     

Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.     

不同偶联剂对白炭黑表面的改性及其表征

采用3种硅烷偶联剂双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、乙基三甲氧基硅烷(11-100)对沉淀法白炭黑粉体进行有机湿法改性。借助傅里叶红外光谱、接触角仪、纳米粒度及Zeta电位仪、扫描电镜等检测手段对白炭黑改性前后的结构及性能进行表征,研究考察3种不同偶联剂对沉淀法白炭黑的疏水性及分散性的影响。结果表明:3种不同硅烷偶联剂都已成功接枝到白炭黑表面,其中Si69改性的白炭黑剩余羟基数与未改性白炭黑表面羟基数的比值最小,为34.23%;经偶联剂改性后的白炭黑,团聚现象减弱,粒径分布变窄,分散性得到改善,疏水性大小依次为Si69-Si O_2KH570-Si O_211-100-Si O_2;综合对比3种偶联剂的改性效果,Si69的改性效果最好。     

Solvent effect on ageing of silica gels

The structure of silica gels derived from tetraethoxysilane (TEOS) with molar compositions of TEOSH₂OHNO₃=1100.4 and then aged in various solvents, was studied. The effect of various solvents having different physical properties on the gel structure, as well as the relationship between the solvent properties and the dried gel structure, were investigated. The density, surface area and pore-size distribution were measured. The results of the pore structure and SEM showed the aged gels to have a slit-shaped micropore, narrow pore-size distribution, and homogeneous microstructure. The density, surface area, pore size and pore volume of dried gels changed as the gels were subjected to ageing in various solvents. The surface area could be related to the polarity parameter of the ageing solvent.     

A facile method to coat mesoporous silica layer on carbon nanotubes by anionic surfactant

This paper described a facile sol-gel method to synthesize silica-coated multi-walled carbon nanotubes (MWCNTs) using anionic surfactant sodium dodecyl sulfate (SDS) for the first time. This method is quite simple and easy to operate, the uniformly silica shell could be a readily controlled ratio of two silane agents of 3-aminopropyltriethoxysilane and tetraethoxysilane, and more suitable for large-scale production. The resulting CNTs@SiO₂ composites are characterized by transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy. It is of interest to note that the mesoporous CNTs@SiO₂ materials can be obtained via the extraction or the calcination process and mesoporous property was investigated by N₂ adsorption-desorption analysis.     

The aluminium effect on gel-derived iron silica glasses

Sol–gel aluminosilicate glasses containing 1 mol% of Fe₂O₃ and different amounts of Al₂O₃ (1; 2; 3; 4; 6 and 8 mol%) have been investigated. The ultraviolet–visible–near infrared spectrophotometry (UV–VIS–NIR), electron paramagnetic resonance (EPR), X-ray diffraction (XRD) and scanning electron microscopy (SEM), has been employed to obtain information about the structural evolution of the samples. The concentration of Al₂O₃, the treatment temperature and the furnace atmosphere play an important role in the structural incorporation of iron. The treatment of the samples, in air and under reducing conditions, results in remarkable changes in the UV–VIS–NIR and EPR spectra. In the samples were detected nanoparticles. The low temperature blocking of the nanoparticles magnetic moments has been clearly evidenced in the EPR derivative spectra at low temperatures.     

The effect of silica nanoparticulate coatings on cellular response

The current techniques used to create patterned materials at the nanometer scale such as electron beam lithography are restricted to patterning small areas, which can be expensive and time consuming. A simple, cost-effective approach has been developed to create a reproducible surface topography to influence the cellular response. In this study, the cellular response of murine fibroblasts to 7, 14 and 21 nm colloidal silica particles were investigated over one, three and seven days and up to seven weeks. The surface topography and wettability of the surfaces were also studied. The results confirmed that silica particles create a nanoscale topography, which initiates a distinctive cellular response affecting the morphology, adhesion and proliferation of the fibroblasts. The effect was evident up to seven weeks with no adverse effects on cell viability.     

The effect of carbon precursor on the pore size distribution of mesoporous carbon during templating synthesis process

The starch and cyclodextrin were selected as the precursors and the mixture of surfactant and tetraethyl orthosilicate (TEOS) as template to prepare mesoporous carbon. The result showed that a bimodal pore size distribution in mesoporous carbon derived from starch appeared; one was around 3.4 nm and the other ranged from 3.8 to 16.2 nm. However, there existed a concentrated pore size distribution from 3.2 to 4.2 nm in mesoporous carbon derived from cyclodextrin. The different molecular structure of starch and cyclodextrin and their polymerization process in the presence of sulfur acid were responsible for the resulted mesoporous carbon structure; the starch could polymerize by head to head or side by side, but the cycleodextrin was only polymerized by head to head.     

利用表面活性剂量改变孔洞率制备的纳米多孔SiO2膜

采用表面活性剂十六烷基三甲基溴化氨(CTAB)为模板剂,在酸性条件下产生多孔结构,再经热处理去除CTAB。实验中使用溶胶?凝胶技术,正硅酸乙酯(TEOS)为硅源,以及二次去离子水,盐酸为催化剂等原料,利用表面活性剂与硅源水解后形成的聚集体相互作用,在溶液中形成分子自组装体,制备前驱体溶胶。通过简单提拉迅速蒸发溶剂制备纳米多孔或纳米介孔SiO2薄膜,分析和研究了表面活性剂浓度对纳米多孔SiO2薄膜的结构和孔洞率的影响,通过操纵表面活性剂的含量,能控制薄膜的纳米结构、孔洞率、孔大小和孔的形态以及膜的形貌。小角度射线衍射、场发射透射电子显微镜、原子力显微镜显示可以制得具有六方、立方和由三维六方和简单立方组成的新相结构以及比介孔大的纳米多孔结构的薄膜。椭偏仪测量得到所制备薄膜的孔洞率为51.8%-65.6%,借助此孔洞率能计算薄膜的折射率和介电常数。     

Infrared method for in situ studies of polymer/surfactant adsorption on silica powders from aqueous solution

This article presents a general infrared spectroscopic method that enables the monitoring of the adsorption of surfactants and polyelectrolytes on high surface area silica particles from aqueous solution. The method is based on the use of a ZnSe internal reflection element (IRE) coated with a layer of titania particles. The titania surface is the converted to silica using atomic layer deposition with sequential addition of an amine catalyst, gaseous SiCl4, and water vapor. A minimum of three cycles is needed to produce a surface that mimics silica, as evidenced by the reaction of hexamethyldisilazane and zeta potential measurements. It is shown that the silicacoated titania particles on the ZnSe crystals are stable to flowing aqueous solutions below pH = 8 and can be used to study the dynamics of polymer/surfactant adsorption on silica.     

Processing effect on structural changes of high acid-catalysed silica gel

The structure of silica gels prepared by hydrolysis of tetraethoxysilane (TEOS) with high acid content has been investigated. The gels were obtained by varying the nitric acid contents at a constant H₂O/TEOS molar ratio of 10. The molar compositions were TEOS: H₂OHNO₃ =110: x(x=0.1–1.0). The effects of acid content and drying temperature on structural changes in the gels were examined. In addition, the surface area, pore volume, pore size distribution, and the microstructure were determined. The results showed that the pore structure changed to larger pore sizes and broader size distributions as a result of increasing the drying temperature. However, at a constant drying temperature, a higher acid content yielded a higher pore volume. The gels dried at lower temperatures had slit-shaped micropores and a narrow pore size distribution; whereas, the gels dried at higher temperatures had ink bottle-shaped pores and a relatively broad size distribution.     

Observation of quantum confinement effect on ZnO embedded mesoporous silica

Nonionic surfactant as liquid organic template and tetraethoxysilane as silica precursor were used for the synthesis of mesoporous silica with ordered arrangement of nanopores (diameters are about 1-6 nm). The synthesized mesoporous silica was used as the template for the synthesis of ZnO nanoparticles using zinc acetylacetonate as ZnO precursor. The as synthesized ZnO incorporated in the mesoporous silica nanocomposite were analyzed using X-ray diffraction, TEM and Photoluminescent spectrum. ZnO introduction has no extensive influence on the mesoporous structure of silica. Quantum confinement effects are observed in the case of ZnO nanoparticles embedded in mesoporous silica. The particle size of ZnO is about 3.2 nm. The band gap is broadening to 3.47 eV.