有序介孔氧化硅孔道氧化锰团簇组装研究

以有序介孔氧化硅MCM-41为主体材料,通过浸渍法及后续热处理工艺,在孔道中组装氧化锰的团簇粒子,并对其进行结构表征。通过XRD、HR—TEM、XPS及N2吸附表明氧化锰的团簇粒子已经成功组装到MCM-41有序孔道中。通过对不同孔径有序介孔材料的氧化锰团簇粒子的组装,表明随着孔道中组装量的增加,350nm附近光致发光强度增强,吸收边发生红移,同时1000nm附近吸收带宽化。     

蒸发诱导自组装仿生合成高有序度三维六方介孔氧化硅薄膜

借鉴自然界生物矿化的形成机理,利用蒸发诱导自组装(EISA)的方法,以十六烷基三甲基溴化铵(CTAB)为结构导向剂,正硅酸乙酯(TEOS)为硅源,通过浸渍提拉在普通玻璃片上制备出高有序度、三维六方结构的介孔氧化硅薄膜,通过XRD、TEM、低温N2吸附/脱附等方法对薄膜进行了表征,并初步讨论了形成三维六方结构的机理.     

Simple synthesis of hierarchically ordered mesocellular mesoporous silica materials hosting crosslinked enzyme aggregates

Hierarchically ordered mesocellular mesoporous silica materials (HMMS) were synthesized using a single structure-directing agent. The mesocellular pores are synthesized without adding any pore expander; the pore walls are composed of SBA-15 type mesopores. Small-angle X-ray scattering revealed the presence of uniform pore structures with two different sizes. Using HMMS as a nanoscopic template, hierarchically ordered mesocellular mesoporous carbon (HMMC) and polymer (HMMP) materials were synthesized. HMMS was used as a host for enzyme immobilization. To improve the retention of enzymes in HMMS, we adsorbed enzymes, and then employed crosslinking using glutaraldehyde (GA). The resulting crosslinked enzyme aggregates (CLEAs) show an impressive stability with extremely high enzyme loadings. For example, 0.5 g alpha-chymotrypsin (CT) could be loaded in 1 g of silica with no activity decrease observed with rigorous shaking over one month. In contrast, adsorbed CT without GA treatment resulted in a lower loading, which further decreased due to continuous leaching of adsorbed CT under shaking. The activity of crosslinked CT aggregates in HMMS was approximately 10 times higher than that of the adsorbed CT, which represents a 74-fold increase in activity per unit weight of HMMS due to higher CT loading.     

Effects of sol aging on mesoporous silica thin films organization

Cetyltrimethylammonium bromide (CTAB) templated mesoporous silica thin films were deposited on glass slides by evaporation-induced self-assembly (EISA) process using a dip-coating method. The effects of sol aging on the mesophase structure of the thin films organization were investigated. Identification of the structures was accomplished by coupling X-ray diffraction (XRD) and transmission electron microscope (TEM) investigations, and corresponding sol was characterized by ²⁹Si solution state nuclear magnetic resonance (²⁹Si NMR) and UV-Vis spectrophotometer for studying the mesophase structure evolution. Results indicate that sol aging has great effects on the mesophase structure of the films organization, which includes degree of order and phase transformation of mesoporous silica thin films. To obtain a better understanding of the effects of sol aging on the mesophase structure, the theories of apparent mass fractal dimension and charge density matching were introduced to explain the self-assembly process.     

有序介孔炭的模板合成进展

以MCM-41为代表的介孔分子筛具有孔道排列规则、孔径分布窄、比表面积高等特点，在催化、吸附、分离等领域具有广泛应用前景，尤其是以其为模板开展的纳米组装科学已成为目前材料研究的热点之一。在简要介绍硅基介孔分子筛的分类和合成机理的基础上，对国内外多孔炭模板合成的研究现状进行了述评，重点阐述了有序介孔炭模板合成的特点、合成工艺、模板类型、碳前驱体的种类及其在双电层电容器、催化、储能等方面的初步应用结果，并展望了有序介孔炭模板合成的发展趋势，指出模板成本的降低、工艺条件的简化和可控化将成为未来一段时期人们研究的重点。     

Facile fabrication of copper-supported ordered mesoporous carbon for antibacterial behavior

Copper-supported ordered mesoporous carbon (Cu/CMK-3) was prepared by impregnating ordered mesoporous carbon (CMK-3) with CuCl₂ aqueous solution. CMK-3 was served as a carrier for the continuous immobilization of Cu. The supported copper was observed to be the bivalence state, indicating that the Cu²⁺ ion was not reduced into cuprous species or metallic copper in the CMK-3. The BET surface area and pore volume of Cu/CMK-3 were 728 m²/g and 0.95 cm³/g, respectively. The antibacterial activities of Cu/CMK-3 were tested by means of minimal inhibitory concentration (MIC) and viable cell counting method. The results show that Cu/CMK-3 presents a good antibacterial performance against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), which indicates its potential applications as antibacterial material for microbiocides.     

罗丹明B在介孔二氧化硅中的发光研究

利用介孔二氧化硅为载体,将罗丹明B(RhB)分子嵌入其中,获得了纳米复合材料。测量了光致发光谱,观察到纳米孔中小分子的光致发光蓝移现象,与不同浓度RhB 无水乙醇溶液的光致发光相比,纳米孔中的RhB的发光接近单分子发光行为,这种现象与纳米孔对有机分子的聚集程度的限制有关。同时观察到纳米复合物的荧光强度远远强于液相染料,初步推断为二氧化硅基质对染料分子产生了能量传递。     

水热法合成介孔氧化硅材料的结构及表面特性

以十六烷基三甲基溴化氨 (CTMABr)为模板剂 ,利用碱性水热法制备了介孔氧化硅材料 ,并采用小角度XRD、HRTEM、BET和FT IR等测试手段研究了其孔的结构、表面N2 吸附特性和孔径分布情况。结果表明 :碱性水热法制得的介孔氧化硅材料具有规则的六方结构 ,介孔的最可几半径为 1 9mm ,比表面积为 5 42 8m2 / g ,孔容为 0 4 5 6cm3/ g。     

单分散纳米介孔二氧化硅的制备

在温和碱性条件下,以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,三嵌段共聚物F127为助剂,制备出粒径为60～80 nm的单分散纳米介孔二氧化硅MCM-41.研究了F127的用量对介孔结构和纳米粒子分散性的影响.结果表明,适量的非离子表面活性剂F127具有助模板剂的作用,可以有效地提高纳米介孔粉体的有序性;过量的F127阻碍六方介孔相的形成,降低样品的有序性.F127与十六烷基三甲基溴化铵的摩尔比在0.04～0.08范围内,可以得到有序性好、孔径均一和孔隙率大的单分散纳米介孔二氧化硅MCM-41.     

Short-period synthesis of ordered mesoporous silica SBA-15 using ultrasonic technique

Mesoporous silica SBA-15 was synthesized from rice husk ash via the ultrasonic technique in the hydrolysis-condensation stage. The effect of the time period in this stage on the mesoporous silica SBA-15 structure and physical properties was investigated and compared with those of the SBA-15 prepared by the conventional technique. It has been shown that the ultrasonic technique can be successfully applied for the synthesis of mesoporous silica SBA-15 with highly ordered hexagonal pore-arrangement and narrow PSD within the much shorter hydrolysis-condensation period. The SBA-15 products synthesized via the ultrasonic technique for the time period of 3 h have higher specific surface area, total pore volume, and microporosity than those prepared by the conventional technique for the time period of 24 h.     

Enhanced microwave absorption properties of Ni-doped ordered mesoporous carbon/polyaniline nanocomposites

We propose and demonstrate a new scheme to improve microwave absorption property through polyaniline (PANI)-functionalized Ni-doped ordered mesoporous carbon (OMC) by in situ polymerization method. The polymer-functionalized nanocomposites, embedding polyaniline within ordered mesoporous carbon, exhibit strong and broadband microwave absorption due to its better dielectric loss characteristic. OMC-Ni0.15/PANI exhibits an effective absorption bandwidth (i.e., reflection loss (RL) ≤ −10 dB) of 4.7 GHz and an absorption peak of −51 dB at 9.0 GHz. The absorption peak intensity and position can be tuned by controlling the thickness of the coating.     

一种松香基双季铵盐和CTAB共混模板介孔SiO2的制备

以一种松香基双季铵盐和CTAB为共混模板,正硅酸乙酯为硅源,通过调节两种表面活性剂的不同用量,在碱性条件下水解制备了SiA、SiB、SiC、SiD4种SiO2材料。采用TGA确定煅烧温度为550℃;SEM照片分析可知SiC、SiD的微观形貌优于SiA、SiB,且为分散均匀的球形颗粒,无团聚;TEM照片分析可知,SiC、SiD为具有介孔结构的球形颗粒;FT-IR确证了SiC、SiD煅烧前后的基本结构;经氮气吸附-脱附实验分析,结果表明,SiC、SiD的孔径主要集中在3.8nm处,比表面积和累积孔体积分别为685.29m2/g、1.22cm3/g和609.73m2/g、0.93cm3/g。     

无机介孔膜的制备和应用

重点介绍了国内外近年来在无机介孔膜的制备与应用方面的最新进展,并对其制备与应用研究前景进行了展望．     

Effect of amino groups of mesoporous silica nanoparticles on CpG oligodexynucleotide delivery

Abstract

In this study, we proposed to modify mesoporous silica nanoparticles (MSNs) with 3-aminopropyltriethoxysilane (NH₂-TES), aminoethylaminopropyltriethoxysilane (2NH₂-TES) and 3-[2-(2-aminoethylamino)ethylamino] propyl-trimethoxysilane (3NH₂-TES) for binding of cytosine-phosphate-guanosine oligodexynucleotides (CpG ODN), and investigated the effect of different amino groups of MSNs on the CpG ODN delivery. Serum stability, in vitro cytotoxicity, and cytokine interleukin-6 (IL-6) induction by MSN-NH₂/CpG, MSN-2NH₂/CpG and MSN-3NH₂/CpG complexes were investigated in detail. The results showed that three kinds of aminated-MSN-based CpG ODN delivery systems had no cytotoxicity to RAW264.7 cells, and binding of CpG ODN to MSN-NH₂, MSN-2NH₂ and MSN-3NH₂ nanoparticles enhanced the serum stability of CpG ODN due to protection by the nanoparticles. However, three aminated MSN-based CpG ODN delivery systems exhibited different CpG ODN delivery efficiency, and MSN-NH₂/CpG complexes had the highest ability to induce IL-6 secretion.     

Novel pathways for the preparation of silica antireflective films: Improvement in mechanical property

Silica antireflective films by the base catalyzed sol-gel process show poor mechanical property. In this study, silica antireflective films with good mechanical property have been prepared by the acid catalyzed templating sol-gel process. The single-layer film was deposited from an acid-catalyzed silica sol solution with polymer F127 incorporation. The silica sol was first dip deposited onto substrate to form films on both sides of the substrate and then subjected to thermal treatment at 500 °C. After thermal treatment, the abrasion resistant antireflective film was achieved due to the formation of porous structure in the resultant film as a result of decomposing F127. Optical spectroscopic measurement shows that the coated glass with maximum transmittance of 99.5% has been obtained. Nanoindenter measurement shows that the elastic modulus and hardness of films are 16 GPa and 1.3, respectively, which are much better than those films derived from base-catalyzed silica sols. The high transmittance and good mechanical property make such films potential in both military and civil applications.     

Gold nanoparticles incorporated mesoporous silica thin films of varied gold contents and their well-tuned third-order optical nonlinearities

Gold nanoparticles (NPs) incorporated mesoporous silica thin films (MSTFs) of varied gold contents from 4.64 to 29.15 wt.% were synthesized through a refined chemical modification to the mesopore surface using different amounts of silane with amino end group. The microstructures of the composite thin films were characterized and the off-resonant third-order optical nonlinearities of the composite thin films were investigated by Z-scan technique at 1064 nm. The resultant composite thin films showed increased third-order optical nonlinear susceptibility (χ⁽³⁾) from 4.26 × 10⁻¹¹ to 9.24 × 10⁻¹⁰ esu at increased gold contents. The dependence of χ⁽³⁾ on gold content have been discussed, which can be described by an exponent function y = y₀ + Ae^−x/t when the gold contents of the composite thin films were below 30 wt.%.     

Evolution of nanocrystallinity in periodic mesoporous anatase thin films

Herein we report the first kinetic study of the intrachannel wall phase-transition of amorphous titania to nanocrystalline anatase for periodic mesoporous titania thin films, monitored by time-resolved in situ high-temperature X-ray diffraction. Structural transformations associated with the phase transition are further probed by high-resolution scanning electron microscopy and transmission electron microscopy. The model found to be most consistent with the kinetic data involves 1D diffusion-controlled growth of nanocrystalline anatase within the spatial confines of the channel walls of the mesostructure. The observation of anisotropic, rod-shaped anatase nanocrystals preferentially aligned along the channel axis implies that the framework of the liquid-crystal-templated mesostructure guides the crystal growth.     

Fabrication of mesoporous silica/carbon black nanospheres and load-sensitive conducting rubber nanocomposites

Mesoporous silica nanospheres (MSNs) with regular pores have been fabricated using cetyltrimethylammonium bromide (CTAB) as surfactant in high pH solution. The average size of the MCM-41 silica nanospheres was reduced from 95 to 48€nm, while the concentration of CTAB increases from 7.7 to 11.5mmol/L. Carbon black was deposited on MSNs using hexane as the carbon source. By mixing such materials with silicone rubber, the composites become conducting when equivalent carbon volume fraction is higher than a certain region, which is less sensitive to the morphology of the deposited carbon. The improved piezoresistance repeatability has been found on the composite sample of MSNs/carbon plus extra high conducting carbon black. The load and strain sensitive range up to 0.35MPa and 0.10, respectively, with less resistance fluctuation during multiple press loading cycles.