双模板法制备介孔／大孔复合孔结构硅胶独石

采用双模板法,向正硅酸甲酯的水解体系中同时引入聚乙二醇和三嵌段共聚物,成功制备出具有双连续大孔、同时孔壁中分布着有序介孔的复合孔结构硅胶独石材料. 产物的比表面积高达880 m2/g, 大孔孔径为0.2～5 μm, 介孔高度集中地分布在 5 nm. 结合物理吸附、扫描电镜、粉末X射线衍射和透射电镜等表征手段,发现合成条件如原料组成、反应温度和pH值等对反应体系中凝胶化转变和相分离发生的相对速度有重要影响,进而影响产物复合孔结构的生成. 此外,通过对合成条件的优化,一方面增强了无机骨架的强度,另一方面降低了湿凝胶干燥过程中的毛细管压力降,有效缓和了凝胶结构在干燥过程中的开裂和变形,使复合孔结构硅胶独石在厘米尺度内具有良好的整体性能.     

Synthesis and characterization of SiC materials with hierarchical porosity obtained by replication techniques

Porous silicon carbide monoliths were obtained using the infiltration of preformed SiO(2) frameworks with appropriate carbon precursors such as mesophase pitch. The initial SiO(2) monoliths possessed a hierarchical pore system, composed of an interpenetrating bicontinuous macropore structure and 13 nm mesopores confined in the macropore walls. After carbonization, further heat treatment at ca. 1,400 degrees C resulted in the formation of a SiC-SiO(2) composite, which was converted into a porous SiC monolith by post-treatment with ammonium fluoride solution. The resulting porous SiC featured high crystallinity, high chemical purity and showed a surface area of 280 m(2) g(-1) and a pore volume of 0.8 ml g(-1).     

Hollow-fiber membranes coated with polymerizable bicontinuous microemulsions

A new method has been successfully employed to prepare hollow-fiber membranes by coating and polymerizing bicontinuous microemulsions onto the internal surfaces of hollow-fiber membranes. The bicontinuous microemulsion consisting of water, a polymerizable zwitterionic surfactant of acryloyloxyundecyl dimethylammonio acetate, methyl methacrylate, and 2-hydroxylethyl methacrylate (HEMA) can form a transparent polymer thin film after polymerization. The hollow-fiber membranes as the supports for microemulsion coatings were fabricated from the spinning solution of polyethersulfone/diethylene glycol/N-methyl-2-pyrrolidone. The microemulsion coated hollow-fiber membranes were evaluated by the separation efficiency and the permeation rate of polyethylene glycol (PEG) solutions. The performance of coated membrane on the PEG separation is strongly dependent on the concentration of HEMA and water in precursor bicontinuous microemulsions. The pore size of the hollow-fiber membranes can be regulated between about 2 to 40 nm by varying the composition of precursor bicontinuous microemulsions. The characteristics of the coated membranes is believed to be directly related to the bicontinuous structures of precursor bicontinuous microemulsions. The use of polymerizable bicontinuous microemulsions enable one to better control the microstructures of coated membranes via in situ polymerization.     

Bicontinuous Nanoporous Frameworks: Caged Longevity for Enzymes

The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three‐ dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme‐loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts.     

Design of highly porous melamine-based networks through a bicontinuous microemulsion templating strategy

Designing low density polymeric porous materials with defined pore sizes (diameters in the 100 nm range) still remains a real synthesis challenge. Here, for the first time, we present a strategy by which bicontinuous microemulsions are used as templating agents for the in-situ aqueous polycondensation of organic resins (melamine formaldehyde, MF). The behaviour of surfactants with different head-groups in systems including oil and MF-containing aqueous phase is studied. While many surfactants are not compatible with aqueous MF precondensates, here we report a non-ionic surfactant either used solely or along with anionic surfactants which prove to be successful at keeping bicontinuous microemulsion systems homogeneous even during early stages of polymerisation. However, upon acid-catalysis it becomes clear that the pore structure of the organic material is largely controlled by the kinetics of phase separation due to the sol–gel process rather than by the thermodynamic equilibrium of the template (microemulsion). Indeed, despite numerous attempts, stabilising the microemulsion interface with zero curvature (bicontinuous) has remained problematic. Instead, we show a new behaviour for the MF resin whereby non-spherical MF morphologies (i.e. thread-like structures) can be obtained by specific interactions between the aqueous amino resin and the acid counterions.     

微乳液聚合制备多孔高吸油甲基丙烯酸酯类树脂的研究

研究了双连续相微乳液聚合制备多孔高吸油树脂,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为共聚单体(油相),水(H2O)/乙醇(EtOH)为混合水相,2,2′-偶氮二异丁腈(AIBN)为引发剂,采用十二烷基硫酸钠(SDS)和复配十二烷基硫酸钠/吐温80(SDS/T80)两种乳化体系,调节油相和水相比例,配制出双连续相微乳液.聚合在无搅拌下进行.研究了乳化体系、混合水相含量、单体配比、交联剂和引发剂用量等因素对树脂吸油性能的影响.结果表明,多孔高吸油树脂比同系无孔树脂的吸油速率大大提高,最快可以在2min内达到吸油饱和.树脂对苯,四氢呋喃,四氯化碳的吸油倍率分别达到15.5g/g,15.5g/g,31.7g/g.     

Preparation of composite membranes with bicontinuous structure

Composite membranes with a hierarchical structure comprising thin regions with a bicontinuous structure and thick regions providing mechanical strength have been prepared by casting inorganic zeolite particles and mixtures that yield organic polymers onto substrates that were decorated with sessile droplets of aqueous solutions. Analysis by scanning electron microscopy (SEM) showed a membrane structure with well-ordered imprints caused by the sessile template droplets. These imprints were open at the bottom and covered on the top with a thin sheet composed of particles and polymer. The particles protruded out of the polymer sheet at the top and bottom of the membrane in the thin regions. A significant number of the particles protruded out of both interfaces at the same time. Thus, these parts of the membrane can be considered to be bicontinuous. The imprints are surrounded by thick regions. These regions act as a supporting structure. Thus, the membranes are stable enough to be handled without special precautions and might be applicable to membrane separation processes.     

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.     

Pore morphologies in disordered nanoporous thin films

Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology.     

Synthesis of water and oil dual-absorption materials by bicontinuous microemulsion polymerization

Water and oil dual-absorption materials for application in oil well cement for self-healing micro creaks has been synthesized through bicontinuous microemulsion polymerization. Bicontinuous structure of microemulsion was used to implement the performance of absorbing both water and oil. Phase behavior of the microemulsion system was analyzed by “ε–β fish-shape phase diagram” from which middle phase line was obtained to provide the formula of polymerization. The product was characterized using scanning electron microscope (SEM), pore size distribution (BET), water/oil absorption rate test and water/oil absorption speed test. SEM analysis showed that neither water absorption component nor oil absorption component formed separated particles, while they formed continuous component respectively. Due to the bicontinuous structure and pores, the materials have fast water and oil absorption rate.     

Polymerised bicontinuous microemulsions as stationary phases for capillary electrochromatography

Summary Polymerisation of bicontinuous microemulsions yields porous monolithic structures with well defined pore sizes that are potentially suitable for use as stationary phases for capillary electrochromatography (CEC). A variety of pore sizes can be achieved by altering the composition of the microemulsion, which typically consists of butyl methacrylate (BMA) and ethylene glycol dimethacrylate (EGDMA) as the polymerisable oil phase. The aqueous phase consists of water, a surfactant (sodium dodecyl sulphate, SDS) and a co-surfactant (1-propanol). 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) is also added to provide charges along the polymer backbone to allow electroosmotic flow (EOF) to occur. SEM analysis shows that in-situ polymerisation yields a monolithic structure with a porous topography. Investigations have shown that these monoliths are easy to prepare, robust and suitable for the separation of phthalates. They generate higher linear velocities than are achieved using the silica based HPLC packings normally used for CEC.     

Synthesis of highly ordered mesoporous crystalline WS(2) and MoS(2) via a high-temperature reductive sulfuration route

A high-temperature reductive sulfuration method is demonstrated to synthesize highly ordered mesoporous metal sulfide crystallites by using mesoporous silica as hard templates. H2S gas is utilized as a sulfuration agent to in situ convert phosphotungstic acid H3PW12O40.6H2O to hexagonal WS2 crystallites in the silica nanochannels at 600 degrees C. Upon etching silica, mesoporous, layered WS2 nanocrystal arrays are produced with a yield as high as 96 wt %. XRD, nitrogen sorption, SEM, and TEM results reveal that the WS2 products replicated from the mesoporous silica SBA-15 hard template possess highly ordered hexagonal mesostructure (space group, p6mm) and rodlike morphology, analogous to the mother template. The S-W-S trilayers of the WS2 nanocrystals are partially oriented, parallel to the mesochannels of the SBA-15 template. This orientation is related with the reduction of the high-energy layer edges in layered metal dichalcogenides and the confinement in anisotropic nanochannels. The mesostructure can be 3-D cubic bicontinuous if KIT-6 (Iad) is used as a hard template. Mesoporous WS2 replicas have large surface areas (105-120 m2/g), pore volumes ( approximately 0.20 cm3/g), and narrow pore size distributions ( approximately 4.8 nm). By one-step nanocasting with the H3PMo12O40.6H2O (PMA) precursor into the mesochannels of SBA-15 or KIT-6 hard template, highly ordered mesoporous MoS2 layered crystallites with the 2-D hexagonal (p6mm) and 3-D bicontinuous cubic (Iad) structures can also be prepared via this high-temperature reductive sulfuration route. When the loading amount of PMA precursor is low, multiwalled MoS2 nanotubes with 5-7 nm in diameter can be obtained. The high-temperature reductive sulfuration method is a general strategy and can be extended to synthesize mesoporous CdS crystals and other metal sulfides.     

Inorganic-Macroion-Induced Formation of Bicontinuous Block Copolymer Nanocomposites with Enhanced Conductivity and Modulus

A facile and electrostatically driven approach has been developed to prepare bicontinuous polymer nanocomposites that is based on the polyoxometalate (POM) macroion induced phase transition of PS-b-P2VP from an initial lamellar phase to a stable bicontinuous phase. The multi-charged POMs can electrostatically cross-link P2VP blocks and give rise to bicontinuous phases in which the POM hybrid conductive domains occupy a large volume fraction of more than 50 %. Furthermore, the POMs can give rise to high proton conductivity and serve as nanoenhancers, endowing the bicontinuous nanocomposites with a conductivity of 0.1 mS cm⁻¹ and a Young's modulus of 7.4 GPa at room temperature; these values are greater than those of pristine PS-b-P2VP by two orders of magnitude and a factor of 1.8, respectively. This approach can provide a new concept based on electrostatic control to design functional bicontinuous polymer materials.     

Tunable synthesis of hierarchical mesoporous silica nanoparticles with radial wrinkle structure

We studied the formation mechanism of hierarchical mesoporous silica nanoparticles with a wrinkle structure (wrinkled silica nanoparticles, WSNs), and a method for substructure control of silica nanoparticles was proposed. We confirmed that WSNs were generated in the bicontinuous microemulsion phase of the Winsor III system. By using the phase behavior of the Winsor III system, which depends on the water-surfactant-oil mixing ratio, and by adding various cosolvents, we could precisely control the structure of silica nanoparticles from the mesoporous to the wrinkle form; furthermore, we could control the interwrinkle distance.     

Inorganic‐Macroion‐Induced Formation of Bicontinuous Block Copolymer Nanocomposites with Enhanced Conductivity and Modulus

A facile and electrostatically driven approach has been developed to prepare bicontinuous polymer nanocomposites that is based on the polyoxometalate (POM) macroion induced phase transition of PS‐b ‐P2VP from an initial lamellar phase to a stable bicontinuous phase. The multi‐charged POMs can electrostatically cross‐link P2VP blocks and give rise to bicontinuous phases in which the POM hybrid conductive domains occupy a large volume fraction of more than 50 %. Furthermore, the POMs can give rise to high proton conductivity and serve as nanoenhancers, endowing the bicontinuous nanocomposites with a conductivity of 0.1 mS cm⁻¹ and a Young's modulus of 7.4 GPa at room temperature; these values are greater than those of pristine PS‐b ‐P2VP by two orders of magnitude and a factor of 1.8, respectively. This approach can provide a new concept based on electrostatic control to design functional bicontinuous polymer materials.     

Hierarchically porous carbon membranes derived from PAN and their selective adsorption of organic dyes

Porous carbon membranes were favorably fabricated through the pyrolysis of polyacrylonitrile(PAN) precursors, which were prepared with a template-free technique-thermally induced phase separation. These carbon membranes possess hierarchical pores, including cellular macropores across the whole membranes and much small pores in the matrix as well as on the pore walls. Nitrogen adsorption indicates micropores(1.47 and 1.84 nm) and mesopores(2.21 nm) exist inside the carbon membranes, resulting in their specific surface area as large as 1062 m2/g. The carbon membranes were used to adsorb organic dyes(methyl orange, Congo red, and rhodamine B) from aqueous solutions based on their advantages of hierarchical pore structures and large specific surface area. It is particularly noteworthy that the membranes present a selective adsorption towards methyl orange, whose molecular size(1.2 nm) is smaller than those of Congo red(2.3 nm) and rhodamine B(1.8 nm). This attractive result can be attributed to the steric structure matching between the molecular size and the pore size, rather than electrostatic attraction. Furthermore, the used carbon membranes can be easily regenerated by hydrochloric acid, and their recovery adsorption ratio maintains above 90% even in the third cycle. This work may provide a new route for carbon-based adsorbents with hierarchical pores via a template-free approach, which could be promisingly applied to selectively remove dye contaminants in aqueous effluents.     

Direct electrochemistry of myoglobin based on bicontinuous gyroidal mesoporous carbon matrix

A strategy of protein entrapment within the bicontinuous gyroidal mesoporous carbon (BGMC) matrix is demonstrated to probe the direct electrochemistry of myoglobin. Large surface area and remarkable electro-catalytic properties of BGMC make it a suitable candidate for high loading of protein molecules and the promotion of heterogeneous electron transfer (ET). In contrast with carbon nanotubes and general carbon mesoporous materials, BGMC is of a relatively isotropic graphited structure and thus can more effectively enhance the heterogeneous ET. Furthermore, a series of BGMCs with different pore sizes (2–7 nm) is designed and synthesized to study the influence of pore size on the immobilization of redox proteins and on the electron transfer.     

Design of hierarchical porous aluminas by using one-pot synthesis and different calcination temperatures

Hierarchical aluminas with pore sizes ranging from a few nanometers to micrometers were obtained using an one-pot sol?Cgel synthesis. The aluminas were synthesized under acid conditions from aluminum isopropoxide in presence of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template and decahydronaphthalene as emulsifier agent. High-resolution transmission electron microscopy, small-angle X-ray scattering, nitrogen physisorption isotherms and mercury intrusion porosimetry provided evidences of porous structure at different hierarchical levels. The produced aluminas possess hierarchical structure composed of different family of pores that coexist in form of cylinders, pyramids and stacking of platelets. The morphology observed by electron microscopy suggests that the cylindrical pores result from the stacking platelets and that the cylinders and pyramidal pores form the walls of macropores of circular section. These aluminas with hierarchical porous architecture present large surface areas (ca. 435?m² g^?1) and pore volumes (ca. 2.1?cm³ g^?1), tunable pore-size distributions and good thermal stability.     

An attempt to detect bicontinuity from SANS data

SANS is a powerful tool to characterise microemulsions, which can have a discontinuous droplet-like structure (oil in water (O/W), water in oil (W/O)) or a bicontinuous one. In the present study, we try to distinguish O/W, W/O and bicontinuous microemulsions by SANS measurements under practical conditions and by a certain evaluation technique. For this reason we chose the well characterised ternary system water-non-ionic surfactant (C(12)E(5))-oil (n-octane), at a fixed surfactant concentration and performed SANS measurements throughout its one-phase channel where droplet-like phases as well as bicontinuous phases are well established. We evaluated the scattering data via the 'Generalised Indirect Fourier Transformation' method (GIFT) which is based on a particulate picture. It should therefore give good results in the droplet domains while a poor fit could be expected for the bicontinuous regime. For comparison we also applied the model of Teubner and Strey (TS) which was developed especially for bicontinuous phases, here a bad fit can be expected for the particulate regime. The data evaluation via GIFT leads to relatively good fits throughout the one-phase channel. The results are physically meaningful and are comparable to those of the TS model. We show that the scattering pattern of a bicontinuous microemulsion can be represented by that of a polydisperse particulate system. This is in clear contradiction to the expectation that the particle picture used in the GIFT method must fail when the bicontinuous regime is reached.