不同酸对介孔二氧化硅球表面形貌和介相结构的影响

在室温、不同酸性条件下合成出微米级球形介孔二氧化硅材料，通过XRD、SEM以及氮气吸附等手段对介孔二氧化硅材料进行了表征。用TEM跟踪不同反应时间介孔二氧化硅球的形成，对这些球颗粒的合成机理进行了讨论，同时探讨了不同酸性条件下介孔二氧化硅表面形貌和介相结构的变化。     

复合介孔二氧化硅膜的制备及应用

复合介孔二氧化硅膜是近十年来发展起来的一种具有独特孔中孔结构的新型膜材料。该材料以多孔膜（无机多孔膜或者有机多孔膜）为硬模板,以表面活性剂为结构导向剂,通过溶胶-凝胶等方法将介孔二氧化硅材料组装在多孔膜的孔道中制备而成。由于其具有不同于传统介孔二氧化硅膜材料的一些独特结构和性能,并在分离、吸附和催化等领域具有广泛的应用前景,引起了人们广泛的关注。本文主要就复合介孔二氧化硅膜的制备方法,特别是近几年内其在纳滤、纳米材料的模板合成、酶的固定、传感器、反应器以及药物释放等方面最新的应用研究进展进行论述,同时对这类新型的复合介孔二氧化硅膜材料在合成和应用方面存在的问题进行了分析和总结,并对其发展前景作了展望。     

以手性两亲小分子为模板剂制备介孔二氧化硅纳米空心球

以L-亮氨酸为手性源合成了手性阳离子两亲性小分子化合物L-18Leu6NEtBr,用其自组装体作为模板,氢氧化钠为催化剂,经溶胶-凝胶过程制备出介孔二氧化硅纳米空心球;分析了介孔二氧化硅纳米空心球的尺寸和孔径.结果表明,所制备的二氧化硅空心球直径约100nm;其介孔孔道平行于壳表面,孔径为3.1nm.     

功能化有序介孔二氧化硅材料在分析样品前处理中的应用

功能化有序介孔二氧化硅材料具有均一可调的介孔孔径、规则的孔道、稳定的骨架结构、易于修饰的内表面和较高的比表面积、高的吸附容量等特性,可用于生物、医药、环境样品等复杂基体中痕量分析物的高选择性分离与富集,因此在样品前处理中的应用特别引人瞩目。文中简要介绍了功能化有序介孔二氧化硅材料的制备方法,综述了功能化有序介孔二氧化硅材料在分离富集金属离子、有机污染物以及生物大分子样品前处理中的应用进展。     

微乳液法合成沸石/介孔二氧化硅复合微球

利用简单微乳液自组装体系, 制备了介孔二氧化硅与Y型或Ti-MWW沸石晶体复合形成的沸石/介孔二氧化硅微球(ZMMS). 硅源正硅酸四丁酯与阳离子型季铵盐表面活性剂形成稳定的O/W微乳液形成大颗粒, 沸石颗粒由于疏水作用而进入油相, 同时, 季铵盐表面活性剂和正硅酸四丁酯组装形成介孔材料. 优化合成条件可以有效控制复合微球的沸石/介孔二氧化硅质量比(0～2.3)和直径(186～965 μm). 两种沸石/介孔二氧化硅复合微球材料的介孔孔径分别为3.98 nm(Y型沸石)和3.75 nm (Ti-MWW型沸石). Ti-MWW沸石/介孔二氧化硅复合微球在液相催化环氧化反应中表现出良好的机械强度, 并且能够达到与Ti-MWW沸石原粉相当的催化活性.     

硬模板法高温水热合成微孔-介孔二氧化硅及掺铝介孔二氧化硅

摘要 采用高温水热合成的方法有利于得到具备高水热稳定性的介孔二氧化硅.本研究中,我们利用α-亚麻酸在加热条件下通过胶束内聚合转化为能够耐受高温水热环境的介观模板,利用此硬模板在高温水热条件下直接合成了微孔-介孔二氧化硅及掺铝介孔二氧化硅.采用了不同的表征手段如X射线衍射（XRD）,氮气吸附,透射电镜等手段对材料进行了表征. 实验结果表明,制得的材料在沸水中处理5天后,仍能保持670m2 g-1的比表面积.透射电镜结果和NLDFT孔径分析结果显示,材料同时具备介孔和微孔结构.29Si MAS NMR谱图显示,完全缩聚的Q4型硅为材料中主要的硅组分,这解释了材料的高水热稳定性.     

载有量子点的介孔二氧化硅微球的制备与性能研究

采用自组装方法制备了一种磁核/介孔二氧化硅壳的微球, 调节体系中C₁₈TMS的加入量可控制介孔硅球的比表面积; 并通过化学修饰的方法对介孔微球表面进行巯基功能化修饰. 利用巯基与量子点之间的相互作用可将一定尺寸的量子点吸附于介孔二氧化硅球的孔中, 令介孔微球具有荧光效应; 同时可以利用吸附不同粒径的量子点的荧光光谱对介孔二氧化硅微球孔径的大小进行近似考察.     

自下而上法制备金-介孔二氧化硅复合纳米管用作还原4-硝基苯酚的催化剂（英文）

采用自下而上方法制备了金-介孔二氧化硅复合纳米管,其中金纳米粒子作为催化剂嵌在介孔二氧化硅纳米管管壁内侧.金纳米颗粒的团聚、脱落和晶粒尺寸生长都可以被有效限制,而且催化剂负载量和尺寸大小均可实现简单控制.管壁中的介孔孔道、纳米管末端开口以及一维中空管道可以协同促进反应物扩散,从而提高4-硝基苯酚还原反应活性.循环实验证明这种复合纳米管催化剂具有良好的可重复使用性,而且在反应过程中未出现金纳米粒子脱落或团聚现象.     

有机-无机杂化介孔二氧化硅在环境保护中的应用

将有机基团通过后嫁接或共缩聚法引入到介孔二氧化硅的孔道表面或骨架中,根据有机基团在材料中的位置可得到表面结合型和桥键型两类功能化介孔材料.本文总结了有机-无机杂化介孔二氧化硅的分类及合成方法,重点介绍了该类材料作为吸附剂在环境保护中的应用,包括金属阳离子、含氧阴离子、有机污染物和气体的去除与回收.并展望了有机-无机杂化...     

有序介孔胺化的聚合物材料的合成及在Knoevenagel缩合反应中的催化性能

通过氯化和胺化等手段对有序介孔聚合物材料(FDU-16)进行功能化, 成功地将胺基引入到介孔聚合物骨架中, 制备出新型有序介孔固体碱催化材料. X射线衍射(XRD)、 氮气吸附-脱附及透射电子显微镜(TEM)表征结果表明, 功能化后的固体碱材料依然保持高度有序性; 红外表征结果表明, 大量的胺基被引入到材料的骨架中. 在Knoevenagel缩合中, 这种新型有序介孔固体碱材料表现出比功能化的介孔二氧化硅等材料更高的催化活性, 这主要归因于其具有较高的比表面积、较强的碱性以及较多的活性中心.     

Silica nanocoils

We report here the results of nanoparticle-catalyzed synthesis of a variety of silica nanocoils (SiNCs) under similar growth conditions to those of making regular straight silica/silicon nanowires (SiNWs). Synthesis of individual SiNCs with alternating coiled and straight segments was achieved with cobalt nanoparticle catalysts at alternating temperatures. In addition, a variety of SiNCs, including multiple SiNCs sharing the same nanoparticle catalyst, SiNC double helices, and individual SiNCs with varying pitches and diameters were made.     

二氧化硅纳米与微米颗粒作为固定化酶载体的生物效应

分别将二氧化硅纳米颗粒(SiNPs)与微米颗粒(SiMPs)作为固定化载体, 选择多聚酶牛肝过氧化氢酶(CAT)和单体酶辣根过氧化物酶(HRP)作为酶模型, 通过考察酶固定化后在酶活回收率、热稳定性、 酶促反应最适温度以及酶在水-有机溶剂混合体系中催化能力的变化, 对载体与酶所产生的生物效应差异进行了系统研究. 酶活回收率结果表明, SiNPs显示出比SiMPs优越的对酶无选择性的高生物亲和性, 而SiMPs则能使固定于其上的酶热稳定性大幅度提高, 且二者都能使固定化酶在有机相中的稳定性得到明显增强. 但酶促反应最适温度的变化结果表明, 对不同类型的酶所产生的生物效应则表现出无规律性.     

利用廉价硅酸盐为硅源合成介孔SiO2球

利用廉价的硅酸盐为二氧化硅前驱体,以非离子和阳离子表面活性剂为混合模板剂合成微米级的介孔二氧化硅。控制非离子和阳离子表面活性剂的量可以得到分散性较好的介孔二氧化硅球,其平均颗粒直径为2．5μm,平均孔径为3．25nm,比表面为1379m^2／g,孔体积高达1．12cm^3／g。实验讨论了两种表面活性剂的比例对介孔二氧化硅形貌和介相结构的影响,并用混合模板机理解释了不同形貌形成的原因。     

Synthesis of UV-Cured Silicone Resin/Silica Nanocomposites from UV-Curable Polysilisiquioxane and Methacrylate-Functionalized Silica

A series of silicone resin/silica polymeric nanocomposites with 0–6 wt% silica content, comprising well-distributed silica nanoparticles in silicone resin matrix, have been synthesized from a UV-curable polysilisiquioxane (UV-PSL) and a methacrylate-functionalized silica via UV-curing in the presence of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) as photoinitiator. To enhance the interfacial interaction, the silica surface was firstly treated with 3-(methacryloxy) propyl trimethoxysilane (MPTS), and its structure was analyzed by FTIR spectrophotometry. The thermal stability of nanocomposites was slightly enhanced with the addition of silica particles. SEM studies indicate that silica particles were dispersed homogenously through the polymer matrix. The physical and mechanical properties such as the thickness, hardness, adhesion, impact strength as well as gloss were examined.     

Mesoporous Silica Applications

Summary: The mesoporous silica have been considered fascinating materials for many techonological applications due to their porous and morphological characteristics. This review focuses on their use as stationary phases for liquid chromatography, supports for immobilizing biomolecules, catalysts, agent for polymer reinforcement and hard templates for the preparation of mesoporous carbons.     

One-Step Synthesis of Monolithic Silica Nanocomposites in Fused Silica Capillaries

The ideal way to prepare efficient, yet robust stationary phases for microanalytical high-resolution methods such as capillary chromatography and electrochromatography remains to be defined. In this contribution a one step sol-gel process is proposed for the production of monolithic, macroporous nanocomposite phases in fused silica capillaries, which require no additional derivatization, since they already bear the interactive (C8) moieties. The effect of the catalyst, the water content, the pH, as well as that of certain additives on monolith formation and porosity is investigated. Volume shrinkage and a tendency to crack were the major obstacles to overcome. Homogeneous stationary phases could be produced by applying a pH gradient during sol formation, thereby changing the catalytic principle from acidic (0.1 M HCl) to basic (gradual formation of OH^– as a consequence of the hydrolysis of N-methylformamide). Gelation/coacervation of suchgels could be induced by the addition of N,N-diethylamine. The water content during sol formation was determined as decisive for pore formation, with 250% of the amount theoretically needed for complete hydrolysis of all precursors giving optimal results. The volume shrinkage problem during xerogel formation was resolved by integrating dialkyldialkoxysilane units (dimethyldiethoxysilane 35 mol%) into the silica network.     

Organofunctional Silica Aerogels

Organically modified silica aerogels were prepared from mixtures of tetramethoxysilane (TMOS) and organofunctional alkoxysilanes RSi(OMe)₃ with R=mercaptopropyl, diphenylphosphinoethyl and chloropropyl. The base catalyzed hydrolysis and condensation reactions, followed by supercritical drying with liquid carbon dioxide were investigated. Starting from 9:1 mixtures of TMOS and RSi(OMe)₃, incorporation of the functional moieties succeeded quantitatively. Increasing the percentage of RSi(OMe)₃ to 20% or 40% leads to an incomplete condensation of the RSiO_1,5 units to the SiO₂ network. Compared with an unmodified silica aerogel, the microstructure of the resulting hybrid aerogels is nearly uninfluenced for the 9:1 mercapto-and chloro-modified samples, while in the phosphino-modified sample the typical pore radii distribution is disturbed by the bulky organic groups. The organofunctional aerogels decompose between 210 and 650°C.     

Thermal Behaviour of Silica Waste from a Geothermal Power Station and Derived Silica Ceramics

The silica waste originating from a geothermal power plant in Mexico was investigated with the aim of finding its applicability as a raw secondary material for ceramics production. The thermal behaviour of the original silica waste (containing NaCl and KCl from marine brine) and of the purified silica was characterized by means of DTA/TG, emanation thermal analysis (ETA) and thermodilatometry (TD). The reactivity of the purified silica waste mixed with CaCO₃ (1.8 mass%) was characterized by means of ETA, DTA and TG. The microstructures and phase compositions of the final products prepared by heating in air were tested by means of X-ray diffraction and of scanning electron microscopy coupled with electron probe X-ray microanalysis. The thermal analysis methods allowed determination of the optimal conditions for thermal treatment of the silica waste in order to obtain partly sintered porous materials for use as refractory bricks. This revised version was published online in August 2006 with corrections to the Cover Date.     

Microcalorimetric Study of Methanol Adsorption on Initial Silica and Silica Modified with Polyfluoroalkyl Groups

The adsorption of methanol on initial silica and modified silica samples containing large mesopores is studied by the adsorption–calorimetric method. The grafted tridecylfluoroalkyl groups have a tilted orientation on the silica and physically screen the part of the surface OH groups that have not been involved in the reaction with a modifier. Adsorbed methanol makes the modifying layer looser, thus facilitating the accessibility of methanol molecules to these hydrophilic adsorption sites. Concentrations of OH groups involved in the chemical interaction with molecules of the modifier, OH groups physically screened by its organofluoric radicals, and OH groups located on the surface areas free of the modifier are quantitatively estimated. An additional silanization of the modified silica leads to coverage of silica surface areas that are free of organofluoric modifier with trimethylsilyl radicals. The heat of interaction between the methanol molecules and silica surface hydroxyl groups is determined; it is equal to 60 kJ/mol. The structure of the modifying organofluoric layer and changes in this structure that resulted from additional silanization of the surface and from the methanol adsorption are discussed.