大孔/介孔多级孔SiO2的制备及其在固定化脂肪酶中的应用

以具有三维骨架结构的环氧树脂大孔聚合物为模板,制备具有毫米级尺寸的大孔/介孔多级孔SiO_2。应用SEM、MIP、FTIR和N_2吸附-脱附法对材料孔道结构和表面性质进行表征。采用吸附法固定褶皱假丝酵母脂肪酶(CRL),研究CRL初始浓度、pH值及固定化时间对脂肪酶固定化的影响,对比研究了游离脂肪酶和固定化脂肪酶的酶学性质。结果表明,大孔/介孔SiO_2具有三维连续贯通的大孔孔道,孔壁由连续的SiO_2纳米薄膜构筑而成且表面存在丰富的介孔,比表面积为75.1m~2/g,孔隙率为92.3%;在CRL浓度为0.6mg/mL、pH值为8.0、固定化时间为10h时,固定化酶酶活达到4 825U/g。与游离脂肪酶相比,固定化脂肪酶的pH稳定性、热稳定性和储存稳定性明显提高,连续使用8次后的酶活为初始酶活的68%。利用环氧树脂大孔聚合物模板制备的大孔/介孔多级孔SiO_2在固定化酶方面具有良好的应用前景。     

气-液界面二元共沉积法制备三维有序大孔SiO2

采用乳液聚合法制备粒径为229nm的单分散聚苯乙烯(PS)微球,以单分散PS微球和粒径为10nm的硅溶胶为原料,采用蒸发自组装法在气-液界面上二元共沉积,制备了大孔SiO2材料。结果表明,当SiO2体积分数为11%时,大孔SiO2材料呈现有序规整的FCC结构,其填充率为42%,收缩率仅为2%。低温N2吸附表明该材料在大孔孔壁上存在6.4nm左右的介孔,是一种具有大孔/介孔复合孔道结构的功能材料。     

A combined top-down and bottom-up approach to fabricate silica films with bimodal porosity

We report a method to fabricate silica films with bimodal porosity based on the surfactant-directed self-assembly process followed by post-treatment with reactive ion etching (RIE). By RIE of a surfactant-templated mesoporous silica film with a 3D hexagonal structure, vertically-etched pores with the size of several tens of nanometers and the depth of ca. 60 nm are generated, while the original caged mesopores (ca. 5 nm in size) are still retained in the unetched parts of the film. Pre-treatment of the mesoporous silica film by wet-etching to expose the pores on the surface, followed by sputter deposition of a Pt layer for partial masking, is crucial for the anisotropic etching of the film. Such a combined top-down and bottom up approach offers an opportunity to fabricate silica films with hierarchical pore architectures.     

Synthesis of mesoporous silica monoliths with embedded nanoparticles

Mesostructured silica-nanoparticle monolithic composites have been synthesized by dispersing prefabricated nanoparticles of gold or zeolite (silicalite) in ethanolic reaction mixtures containing SiCl4 and a Pluronic triblock copolymer template. Whereas silicalite nanoparticles were used directly, surface functionalization of the gold nanoparticles with either primed silicate ions or a discrete 3-5-nm-thick silica shell was required to increase the interfacial compatibility with the hydrophilic poly(ethylene oxide) blocks. Under these conditions, the resulting monoliths consisted of distributed nanoparticles within an ordered mesostructured silica matrix. Removal of the polymer template by calcination produced corresponding mesoporous silica-nanoparticle replicas. The combination of the structure and the porosity of the silica framework with the crystal chemical properties of the embedded nanoparticles suggests that such composites should be useful as multifunctional materials.     

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.     

Preparation of in-situ Pt nanoparticles into frameworks of mesoporous silica for improving thermal stability

The Pt/sulfur-containing mesoporous silica (SMS) was obtained through in-situ co-condensation of TESPTS and TEOS in the presence of a triblock copolymer template. Strong interaction between the Pt NPs and S moieties of TESPTS in the SMS frameworks played an important role in the stabilization of Pt NPs against the sintering or coalescence problems. The Pt/SMS significantly improved the thermal stability at high temperature.     

A controlled formation of cage-like nanoporous hollow silica microspheres

Cage-like hollow silica microspheres composed of mesoporous silica nanoparticles and macroporous interparticle voids were fabricated via the latex-surfactant dual templates route, simply by controlling the surfactant additions below its critical micelle concentration. The surface area, pore volume increase, and both the mesopore and macropore sizes decrease with the increase in surfactant amount. The surfactant cations preferentially assemble with negatively charged silica species generated by the hydrolysis and condensation of tetraethyl orthosilicate to form composite silica-surfactant nanoparticles. The electrostatic repulsion between the silica-surfactant composite nanoparticles and negatively charged polystyrene (PS) beads is smaller than that between surfactant-free silica and PS, favoring the deposition of composite nanoparticles on the surface of PS template. In the meantime, the deposited nanoparticles also have reduced repulsion from their neighbors, favoring their bridging to form silica shells. The more the surfactant is used, the less the repulsion exists among the composite particles and the smaller the interparticle macroporous voids are.     

Fabrication of highly ordered nanoscale poly (lactic acid) surface based on self-assembled silica microspheres

A simple process was developed to fabricate poly (lactic acid) (PLA) film possessing a highly ordered nanoscale surface. For the first step, an array of silica microspheres was prepared by self-assembly on a completely hydrophilic silicon wafer. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images showed that a highly ordered array was formed, and then this array was used as the template for fabricating polymer film with highly ordered nanoscale surface. Next, a PLA solution was spin coated on the template. After solidifying, silica microspheres were embedded in the thin layer of PLA, maintaining their highly organized structures. Finally, silica microspheres were etched away by hydrofluoric acid, and only the PLA film with a close-packed hexagonally pattern structure was left on the silicon wafer substrate.     

Aerosol-assisted synthesis of thiol-functionalized mesoporous silica spheres with Fe3O4 nanoparticles

Thiol-functionalized mesoporous silica spheres having Fe3O4 nanoparticles are fabricated in one-pot by aerosol-assisted synthesis. A TEM image shows that Fe3O4 nanoparticles are successfully embedded within the mesoporous silica spheres. SEM images and SAXS profiles reveals that the encapsulating Fe3O4 nanoparticles do not affect the ordering of a mesoporous structure. The spherical morphologies are also well retained. The presence of cage-type mesopores with uniform size is confirmed by N2 adsorption-desorption isotherms and TEM observations. The spray-dried thiol-functionalized particles with Fe3O4 nanoparticles effectively adsorb mercury (II) ions due to their strong interaction to thiol groups embedded in the framework. The particles with the amount of Fe3O4 nanoparticles (3.5 wt%) show a saturated magnetization (over 1.0 emu/g). This magnetic property is useful for practical collection with magnet.     

静电纺介孔氧化硅基纳米纤维的研究进展

介孔氧化硅是最为典型的介孔材料,其具有比表面积高、孔径均一、易于表面修饰等优异特性,广泛应用于吸附分离、催化、传感以及物质负载与缓释等领域。关于粉体和薄膜形态的介孔氧化硅已有大量报道,但纤维形态,特别是连续纤维形态的介孔氧化硅材料的制备仍然是一项挑战。近年来随着静电纺技术的发展,连续纤维形貌的介孔氧化硅材料的制备取得了重要进展。根据纤维介孔结构的有序度和介孔结构引入方式的不同,对静电纺介孔氧化硅基纳米纤维进行详细的介绍。     

介孔SiO2孔道结构对聚酰胺反渗透复合膜性能的影响

在界面聚合过程中,通过添加改进水热方法制备的球形介孔SiO2纳米材料,制备了改性的聚酰胺反渗透复合膜。使用扫描电镜、X射线衍射和氮气吸附-脱附等手段对制备的介孔SiO2纳米材料进行表征;采用反渗透膜评价装置、原子力显微镜、扫描电镜(SEM)和静态接触角仪器等手段对复合膜的性能和结构进行测试和表征;并对比了相同粒径大小的实心SiO2和介孔SiO2对膜渗透性能的影响。结果证明:成功合成了一种具有孔径分布均匀、粒径均一、比表面积较大、分散性较好的介孔SiO2纳米球形颗粒;SEM表征结果证实纳米材料在膜表面分布均匀,膜表面亲水性能提高,粗糙度变大;膜性能测试结果证实了介孔SiO2的添加使得膜在维持较高截留率的前提下,具有更高的水通量;同时,通过对比相同尺寸的实心SiO2作为添加材料,证实了介孔SiO2的孔道结构更有利于水分子的传输。当介孔SiO2添加质量为0.06%时,水通量由23L/(m2·h)提高至39L/(m2·h),对氯化钠的截留仍然维持在98%以上。     

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors

Abstract

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g^-1 at a 20 mV s^-1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles.     

Facile synthesis of ordered mesoporous silica with high γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> loading via sol-gel process

A series of ordered mesoporous silica loaded with iron oxide was synthesized by facile one-step sol-gel route using Pluronic P123 as the template, tetraethylorthosilicate as the silica source, and hydrated iron nitrite as the precursor under acid conditions. The as-synthesized materials with Fe/Si molar ratio ranging from 0.1 to 0.8 were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), and N₂ adsorption porosimetry. All samples possess ordered hexagonal mesoporous structure similar to SBA-15, with a high surface area, large pore volume, and uniform pore size. Although higher iron content causes a distortion of hexagonal ordering structure to some extent, the materials still maintain the ordered mesopore structure even with Fe/Si molar ratio as high as 0.8. Pore structure and TEM data suggest that iron oxide nanoparticles are buried within the silica wall, and increasing the iron oxide loading has little effects on the pore structure of the mesoporous silica. VSM results show as-synthesized samples exhibit superparamagnetic behavior.     

Synthesis and characterization of ordered and cubic mesoporous silica crystals under a moderately acidic condition

Ordered and cubic mesoporous silica materials were synthesized by using poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer as template under a moderately acidic condition of 0.5 mol/l HCl solution. These mesoporous materials were characterized by Fourier transform (FT) IR spectroscopy, thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption–desorption measurements. The three-dimensional cage-like microporosity of the prepared mesoporous silica having ordered hexagonal mesoporous structure was evidenced by the well-defined XRD patterns combined with TEM photographs. SEM observation shows a highly regular cubic crystal structure for the prepared mesoporous silica. The size of these crystallites was maintained within the range between 4 and 6 μm, which is fairly important for the application to the stationary phase for separation. The nitrogen adsorption–desorption analysis reveals that the prepared mesoporous silica possesses a small pore diameter of 3.68 nm, a total surface area of 363.648 m²/g, a total pore volume of 0.379 cm³/g, and a pore-wall thickness of 6.63 nm. These features may lead to higher thermal and hydrothermal stability, excellent microporosity, and good connectivity. The mesoporous silica prepared in this study exhibits potential applications to catalysis, sensoring, and separation.     

Third-order optical nonlinearity of cadmium sulfide nanoparticles loaded in mesostructured silica materials

Cadmium sulfide nanoparticles have been successfully incorporated in three forms of CTAB-templated mesoporous silica materials: one is the mesoporous silica spheres suspended in ethanol solution, the other is the mesoporous silica spheres spin-coated on glass slide, and the third is the dip-coated mesoporous silica thin film. The mesostructures were characterized by XRD and TEM, respectively. Linear optical properties were investigated using UV-visible spectra, and the diameter of the incorporated CdS nanoparticles was measured to be around 3.1 nm. Z-scan technique manifested that these three composites exhibited distinct third-order optical nonlinearities due to the different preparation techniques. Reverse saturation absorption could be detected in the CdS-loaded mesoporous silica spheres suspended in solution, while those dispersed on glass slide presented saturation absorption. The difference in nonlinear absorption of the two mesoporous silica sphere samples could be attributed to defect-related transitions. On the contrary, the CdS-loaded mesoporous silica thin film showed self-defocusing behavior with no nonlinear absorption signals. Compared to that of the CdS nanoparticles with larger size previously reported, the intrinsic microscopic third-order nonlinear optical susceptibility of those incorporated in CTAB-templated mesoporous thin film was increased as predicted by the quantum theory, and the third-order optical nonlinearity was further determined to arise from intraband transitions induced by quantum confinement.     

Disordered mesoporous silica low-k thin films prepared by vapor deposition into a triblock copolymer template film

Mesoporous silica films have been prepared by a vapor phase method using tetraethoxysilane (TEOS) in a batch reactor and in a continuous flow reactor. The TEOS molecules penetrated into a triblock copolymer films and then a triblock copolymer/silica composite structure was formed. A two dimensional grazing-incidence small angle X-ray scattering pattern and field emission scanning electron microscopy images of the films indicated that the films possess ordered and disordered regions. The tortuous pore channels in the wormhole-like disordered structure run parallel to the film surface. The mesostructured triblock copolymer/silica composite films were treated with a trimethylethoxysilane (TMES) vapor before and after calcination. The vapor infiltration treatments effectively improved mechanical strength and hydrothermal stability of the films. The dielectric constant of the TMES-treated mesoporous silica films was reduced into the 1.5–1.7 range.     

钛掺杂对介孔硅材料结构性能的影响

在室温碱性条件下合成了Ｔｉ掺杂的介孔硅材料ＭＣＭ－４１,借助ＸＲＤ,ＩＲ、ＨＲＥＭ和Ｎ２吸附等分析手段,探讨了Ｔｉ掺杂量对介孔材料结构和性能的影响。结果表明：掺杂的Ｔｉ离子可以进行Ｓｉ骨架,并生成Ｓｉ－Ｏ－Ｔｉ键。     

Functionalized cubic mesostructured silica films

Cubic Pm3n mesoporous silica films have been prepared on silicon wafers and quartz crystal microbalance (QCM) devices covered with gold electrodes by a spin-coating process from preformed silica/CTABr/ethanol/water assemblies under acidic conditions. Post-synthesis functionalization of mesoporous films with amino- and thiol-containing organosilanes is performed in order to modify the mesoporous surface for further confinement of nanoscale structures. The type of mesophase structure and the functionalization process was followed with surface sensitive techniques such as grazing incidence diffraction (GID), reflection-absorption FT-IR spectroscopy and gravimetric measurements by applying QCMs technique. Nitrogen sorption data using QCM devices were obtained for the calcined and functionalized mesoporous films.     

Printable and flexible macroporous organosilica film with high protein adsorption capacity

An approach for creating a flexible and macroporous silsesquioxane film using phase separation method is described. The porous film was prepared by a simple coating method where sol-gel solution containing polyacrylic acid (PAA) and 1,6-bis(trimethoxysilyl)hexane in water was applied on boehmite silica coated polymethylmethacrylate (PMMA) film. After drying, the water soluble PAA template was removed by washing the film with water revealing the porous film. With certain ratios of PAA and water, fully co-continuous pore system with open surface was obtained. Porous films with 3-4 μm thickness were found to be highly flexible. The biocompatibility of the porous film was tested by immobilizing a high affinity biotin-binding chimeric avidin (ChiAVD(I117Y)) into the porous matrix The porous film was found to adsorb higher amounts of functional chimeric avidin compared to the pure PMMA film or a boehmite silica coated PMMA film.     

Sol–gel synthesis and characterization of mesoporous yttria-stabilized zirconia membranes with graded pore structure

Mesoporous yttria-stabilized zirconia (YSZ) membranes can be used for liquid phase applications in harsh environments and as supports for ultra-thin dense ceramic, carbonate, or metallic membranes. This article reports on the synthesis and characterization of three-layer mesoporous ceramic membranes consisting of a mesoporous YSZ layer, a macroporous YSZ intermediate layer, and macroporous α-alumina support. The macroporous YSZ intermediate layer was coated on the alumina support using a suspension of submicron-sized YSZ powders, and the mesoporous YSZ layer was obtained by dip-coating with diluted zirconia sol doped with yttrium nitrate. The mesoporous YSZ layer has desired cubic phase structure. Crack-free mesoporous YSZ membranes could be obtained by multiple dip-coating, drying, and calcination using a dilute YSZ sol at a concentration of 0.014 M with the help of using a drying control chemical additive. The 5 times dip-coated mesoporous YSZ membranes were about 1 μm in thickness with an average pore diameter of 3 nm. The mesoporous YSZ membranes exhibited Knudsen separation factor. The characteristics of the dip-coating process for the mesoporous YSZ membranes on the macroporous YSZ support are similar to those on the macroporous alumina support.