以卵磷脂为手性添加剂制备手性介孔二氧化硅

以十六烷基三甲基溴化铵(CTAB)的自组装体为模板,卵磷脂(PC)为手性添加剂,在n_PC:n_CTAB=1:21时,通过溶胶-凝胶法制备了螺旋介孔二氧化硅纳米棒。利用扫描电镜(FESEM)、透射电镜(TEM)、X-射线衍射以及氮气吸附-脱附等测试手段,对该纳米棒的形貌以及孔结构进行了表征。TEM显示该纳米棒的长度约为50~200nm,直径约为30~50nm。X-射线衍射表明孔道呈二维六方排列,虽然FESEM显示纳米棒左右手比例约为1:1,但通过圆二色谱表征证明该纳米棒在埃尺度下倾向于形成单一手性。结果表明,卵磷脂的手性可以传递到螺旋介孔二氧化硅纳米棒中。     

以联二萘酚衍生物为手性添加剂制备介孔二氧化硅

通过溶胶-凝胶法以十八烷基三甲基溴化铵(STAB)自组装体为模板和非离子型联二萘酚衍生物(S)作为手性添加剂制备螺旋介孔二氧化硅。样品利用扫描电镜、透射电镜、X-光衍射以及氮气吸附-脱附进行了表征。结果表明:反应混合物中S与STAB的物质的量之比对介孔二氧化硅的形貌及孔结构有很大影响。改变nS∶nSTAB比,从0.1∶1到0.4∶1时,其结构从螺旋纳米棒状变为表面具有环形层状孔的纳米棒,孔道由沿着纳米棒长轴方向转变为同心环状。当nS∶nSTAB=0.5∶1时,得到类似皱缩花瓣的纳米颗粒。该手性添加剂的引入并没有改变左右手螺旋纳米棒的比例。     

以联二萘酚衍生物为手性添加剂制备介孔二氧化硅

通过溶胶-凝胶法以十八烷基三甲基溴化铵（STAB）自组装体为模板和非离子型联二萘酚衍生物（S）作为手性添加剂制备螺旋介孔二氧化硅。样品利用扫描电镜、透射电镜、X-光衍射以及氮气吸附-脱附进行了表征。结果表明：反应混合物中S与STAB的物质的量之比对介孔二氧化硅的形貌及孔结构有很大影响。改变n_S：n_STAB比,从0.1：1到0.4：1时,其结构从螺旋纳米棒状变为表面具有环形层状孔的纳米棒,孔道由沿着纳米棒长轴方向转变为同心环状。当n_S：n_STAB=0.5：1时,得到类似皱缩花瓣的纳米颗粒。该手性添加剂的引入并没有改变左右手螺旋纳米棒的比例。     

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.     

管壁具有球形介孔的左手螺旋二氧化硅纳米管的制备

通过双模板方法合成了一种管壁具有球形介孔的单手螺旋二氧化硅纳米管.其中,手性两亲性小分子的自组装体控制纳米管的形貌,三嵌段共聚物F127控制管壁中介孔结构和孔径.并借助透射电子显微镜、扫描电子显微镜、多通道物理吸附与孔径分布仪和X-射线多晶衍射分析方法对样品进行了表征.结果表明,此材料的比表面积高达799m2/g,孔径大约是5.7nm.     

原位限域合成介孔碳负载四氧化三铁纳米颗粒

利用废弃蟹壳做模板制备的具有均一孔道结构的介孔碳材料做载体,在孔道内限域原位合成四氧化三铁氧化物纳米颗粒。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射(XRD)表征了材料的结构和性能。 结果表明,孔道结构呈整体式结构,孔直径在40~50 nm,长50~200 μm。 纳米颗粒为四氧化三铁,粒径在10 nm左右,尺寸单分散性好,可均匀分散在介孔孔道内。 该方法工艺路线简单,绿色环保。     

双模板法合成介孔/大孔二级孔道碳材料

以酚醛树脂低聚物为前驱物, 利用双模板法制备了具有介孔/大孔双孔结构的碳材料. 其中以二氧化硅蛋白石为大孔模板, 以嵌段共聚物自组装结构为介孔模板. 对样品进行了扫描电子显微镜(SEM), 透射电子显微镜(TEM), X射线衍射(XRD)和氮气吸附-脱附实验表征. 结果表明所制备的双孔碳材料大孔直径约为230 nm, 介孔直径10 nm.     

以花瓣为模板制备TiO2分层介孔纳米片

以月季花花瓣为模板, 经钛盐溶液浸渍后煅烧, 合成了新型TiO2 分层介孔纳米片. 采用X射线衍射(XRD)、 场发射扫描电子显微镜(FESEM)、 环境扫描电子显微镜(ESEM)、 透射电子显微镜(TEM)、 紫外-可见漫反射光谱(UV-Vis/DRS)和氮气吸附-脱附曲线分析等手段对样品进行了表征. 结果表明, 所得样品由厚度约4 nm的具有生物形态结构的锐钛矿型TiO2 纳米片组成. TiO2 薄层表面存在大量介孔, 其孔径集中分布于4 nm左右. 由紫外-可见漫反射吸收光谱可知, 材料的吸收边较纳米TiO2 (P25)红移了约20 nm, 因而具有更高的可见光光催化活性. TiO2 分层介孔纳米片在阳光下表现出较强的光催化活性, 在90 min内对亚甲基蓝的降解率可达98%, 远高于TiO2 纳米粉.     

巯丙基功能化介孔纳米二氧化硅的合成

用三种不同的方法将巯基丙基三甲氧基硅烷(MPTMS)引入二氧化硅网络中, 合成了粒径为50-200 nm的巯丙基功能化的介孔纳米二氧化硅, 并利用透射电子显微镜, 热重分析等手段对其形貌与性能进行了表征. 在巯丙基官能团的作用下介孔纳米二氧化硅的形貌发生了重大改变, 由非常规则的六角形变为纳米棒. 控制反应时间可以调节介孔纳米二氧化硅的粒径大小, 用三乙醇胺代替氢氧化钠可以合成直径在100 nm以下的功能化介孔二氧化硅粒子. 为了保护巯基官能团, 选用了酸醇提取法去除模板. 另外, 对介孔二氧化硅粒子的形成机制也进行了探讨.     

手性纳米二氧化硅的制备和应用

由于在手性识别、手性分离以及手性催化等领域的潜在应用,手性纳米二氧化硅已经成为介孔二氧化硅材料发展的重要方向之一。人们通过设计不同的模板分子(包括凝胶因子、表面活性剂、嵌段聚合物及生物大分子等)、控制反应过程的参数等方法已经制备出不同形貌和不同功能化的手性纳米二氧化硅,但形貌可控、手性单一的纳米二氧化硅的制备仍然是该领域的极大挑战。本文对近年来手性纳米二氧化硅的制备及其应用的研究进展作一简单概述。     

Facile synthesis of mesoporous silica nanoparticles with controlled morphologies using water–acetone media

Mesoporous silica nanoparticles with controlled morphologies including nanococoons, nanorods and nanospheres have been synthesized in water–acetone media at room temperature using cetyltrimethylammonium bromide (CTAB) as the template. The obtained nanoparticles generally show hexagonal-like mesoporous structures with average pore size ranging from 2.7 to 3.3 nm and surface area from 806 to 1055 m²/g, respectively. It was found that the changes in water-to-acetone molar ratios have a dramatic impact on the morphologies of the mesoporous silica with different surface roughness, probably due to the solvent influence on the rate of the hydrolysis of tetraethoxy silane (TEOS) and the polymerization of inorganic species. Interestingly, the morphology of the mesoporous silica products can be controlled in shape from nanococoons to nanorods to nanospheres just by decreasing the water-to-acetone molar ratio from 75 to 30 to 15, respectively. From transmission electron microscopy (TEM) images, it was observed that mesoporous parallel channels run along the short axis in some areas in the nanorods, whereas the radially arranged mesopore channels are present in the nanospheres. Additionally, hydrothermal treatment leads to rougher surfaces while retaining the morphologies and nanostructures of these mesoporous silicas.     

Synthesis of hollow spherical silica with MCM-41 mesoporous structure

Hollow spherical mesoporous silica was synthesized by using sodium silicate as a precursor and a low concentration of cetyltrimethylammonium bromide (CTAB) (0.154 mol dm^–3). The resulting hollow spherical particles were characterized with scanning electron microcopy (SEM), small-angle X-ray diffraction (SXRD), transmission electron microscopy (TEM), and N₂ gas adsorption and desorption techniques. The results showed that regular spherical mesoporous silica could be obtained only if the molar ratio of propanol to CTAB was in the range of approximately 8:1–9:1. The spherical particles were hollow (inside), and the shell consisted of smaller particles with a pore structure of hexagonal symmetry. With an increase of the molar ratio of propanol to CTAB, the distance (a value) between centers of two adjacent pores increased, and the pore structure of mesoporous silica became less ordered. N₂ adsorption–desorption curves revealed type IV isotherms and H1 hysteresis loops; with an increase of the molar ratio of propanol to CTAB, the pore size with Barrett–Joyner–Halenda (BJH) diameter of the most probable distribution decreased, but the half peak width of the pore size distribution peak increased     

Preparation of Mesoporous 1,4‐Phenylene‐silica Nanorings through a Dual‐templating Approach

Mesoporous 1,4‐phenylene‐silica nanorings were prepared using cetyltrimethylammonium bromide (CTAB) and (S)‐2‐methyl‐1‐butanol as a chiral dopant in concentrated aqueous NH₃ solutions. Transmission electron microscopy images of the samples indicated that the nanorings were formed by bending nanorods 360°. With increasing the stirring speed or the (S)‐2‐methyl‐1‐butanol/CTAB molar ratio, the morphologies of mesoporous 1,4‐phenylene‐silicas changed from helical nanofibers to nanorings, and then to nano‐saddles. Circular dichroism spectra of these hybrid silicas indicated that they were chiral.     

Characterization Studies on the Ionic Liquid-Templated Mesoporous Silica with Wormlike Pores

This article reports a novel preparation of wormlike mesoporous silica with 1-hexadecane-3-methylimidazolium bromide (C₁₆MIM)Br, a kind of room-temperature ionic liquids (RTILs), as a template via a sol-gel nanocasting technique. The characterization studies were carried out in contrast with that of the mesoporous silica with cetyltrimethylammonium bromide (CTAB), a usually used template, which has the same alkyl chain length with (C₁₆MIM)Br. The structures of the silica materials have been characterized by Transmission electron microscopy (TEM), High-resolution TEM (HRTEM) and N₂ adsorption-desorption measurements. The results show that both the mesoporous materials prepared with different templates respectively can form regular wormlike mesopores with ca. 2 nm in pore diameter. They also have large BET surface areas with narrow size distribution. Compared to the CTAB-template mesoporous silica, the material with (C₁₆MIM)Br as a template has highly uniform pore size and larger surface area. In addition, the formation mechanism of the wormlike mesopores with RTIL has been proposed by an electrostatic charge matching assembly-pathway and steric factor.     

二元阴阳离子表面活性剂法合成介孔氧化硅囊泡

以十二烷基磺酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)为表面活性剂, 在SDS与CTAB的摩尔比为1.0~2.3时, 以正硅酸乙酯(TEOS)为硅源, 在氨水-水体系中于68℃下合成介孔氧化硅囊泡. 通过透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 热重分析仪(TGA)和氮气吸附-脱附实验仪对合成的产物进行表征. 结果表明, 合成的产物为介孔氧化硅囊泡聚集体, 孔径约为4 nm, 样品的Brunauer-Emmett-Teller(BET)比表面积为826 m²/g. 对介孔氧化硅囊泡的形成机理做了初步探讨.     

Effect of salts on synthesis of mesoporous materials with mixed cationic and anionic surfactants as templates

Mesoporous silica materials were synthesized using tetraеthoxysilane as precursor and liquid crystals formed in aqueous mixtures of cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) as templates, without and with the addition of NaBr or Na₂SO₄. For this purpose, the formation of liquid crystals as a function of the ratio of CTAB and SDS under different conditions was studied. It was found that liquid crystals formed in the mixed system of CTAB and SDS at certain mixing ratios are well-structured templates for the synthesis of mesoporous silicas. The synthesized silica materials were characterized by transmission electron microscope and nitrogen adsorption/desorption analysis. The pore size of mesoporous silicas could be controlled between 3 to 6 nm by simply changing the concentration of NaBr in solution. The mesoporous silicas exhibited lamellar structure and the order of structural arrangement was promoted with addition of NaBr. However, addition of Na₂SO₄ led to ink-bottle type pores of mesoporous silica with a narrow pore size distribution of around 2 nm and a higher specific surface area of 610 m² g^–1.     

Preparation of mesoporous submicrometer silica capsules via an interfacial sol-gel process in inverse miniemulsion

Mesoporous silica capsules with submicrometer sizes were successfully prepared via the interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) in inverse miniemulsion by using hydrophilic liquid droplets as template. The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via sonication by using poly(ethylene-co-butylene)-b-poly(ethylene oxide) (P(E/B)-PEO) or SPAN 80 as surfactant. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed by the deposition of silica on the surface of droplets. The formation of capsule morphology was confirmed by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The mesoporous structure was verified by nitrogen sorption measurements. The specific surface area could be tuned by the variation of the amount of cetyltrimethylammonium bromide (CTAB) and TEOS, and the pore size by the amount of CTAB. The influences of synthetic parameters on the particle size and morphology were investigated in terms of the amount of CTAB, pH value in the droplets, TEOS amount, surfactant amount, and type of solvent with low polarity. A formation mechanism of silica capsules was proposed.