以阴离子表面活性剂/阳离子聚铵复合胶束为模板合成有序介孔二氧化硅

基于静电作用, 阴离子表面活性剂可与阳离子聚铵组装形成复合胶束. 借助阳离子聚铵,复合胶束可以作为模板与硅源协同组装, 形成高度有序的介孔二氧化硅. 本文通过调变不同种类阴离子表面活性剂、合成体系pH值、合成温度及阳离子聚铵和硅源用量等因素, 合成了具有不同介观结构和形貌的介孔二氧化硅. 实验证实阴离子表面活性剂/阳离子聚铵复合胶束模板法是合成介孔二氧化硅的一种通用方法.     

阴离子表面活性剂为模板合成双重介孔结构二氧化硅

本文报道以阴离子表面活性剂十二烷基肌氨酸钠为模板,合成具有层状结构和蠕虫状介观结构的双重介孔二氧化硅颗粒．这些颗粒的尺度在300～50011111,氮气吸附表明其比表面为536m^2/g,孔体积为0．83cm^3／g,具有3nm和12nm的双重介孔分布．层状结构形成可归因于表面活性剂形成的层状液晶相模板,而无序蠕虫相是由表面活性剂柱状液晶相模板诱导形成的．层状液晶相的产生可归因于部分质子化的羧酸表面活性剂诱导的柱状相到层状相的转化．     

聚丙烯酸控制合成的聚合物/二氧化硅复合纳米球

以3-氨丙基三甲氧基硅烷(APMS)和正硅酸乙酯(TEOS)为硅源, 与阴离子聚合物聚丙烯酸(PAA)链之间通过S^-N⁺-I^-机理组装合成了聚丙烯酸-二氧化硅(PAA/SiO₂)复合纳米球. SEM, TEM, TG和FTIR表征结果表明, 合成的纳米球是聚丙烯酸和二氧化硅复合物, 平均直径约为80 nm. 在合成PAA/SiO₂复合纳米球的体系中, 加入不同量的有机溶剂THF能够调控复合球的尺度.     

以聚合物乳胶为模板经表面引发原子转移自由基聚合制备空心二氧化硅纳米微球

均匀的空心纳米及微米球因具有可裁剪结构及良好的光学性能和表面性能,而具有非常广泛的应用前景,空心胶囊是一类重要的材料,它是通过不同的化学和物理方法,直接除去壳-核粒子的内核而获得的,目前主要是通过控制表面沉积。或利用静电相互作用层层组装。制备空心胶囊,但前者易于产生独立的无机粒子沉淀,后者的步骤太过繁琐。     

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.     

以短链季铵盐/脂肪酸盐为模板合成超微孔二氧化硅

超微孔材料具有1~2 nm的孔径,在分离、催化应用中有望展现出择形催化的能力。 寻找经济、简便的合成超微孔材料的表面活性剂体系是一项有意义的工作。 本研究以短链季铵盐(十烷基三甲基溴化铵,记为C₁₀TAB)和不同链长脂肪酸酸盐混合胶束为模板剂,硅酸钠为硅源,成功制备出高度有序超微孔SiO₂。 通过小角X射线衍射、N₂吸附-脱附、傅里叶变换红外光谱、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术手段对产品的结构和性能进行了表征。 结果表明,合成体系中脂肪酸盐碳链长、加入量、晶化温度等对产物孔道有序性有很大影响。 当选择正辛酸钠(SO)为助表面活性剂,当n(C₁₀TAB):n(Na₂SiO₃):n(SO):n(H₂O)=1:1.5:0.3:800,晶化温度为80 ℃时,可以得到高度有序超微孔SiO₂。 煅烧后样品比表面积为1300 m²/g,孔体积0.49 cm³/g,孔径分布在1.90 nm。     

中空纳米二氧化硅微球的制备及表征

本文介绍了一种制备中空纳米二氧化硅微球的新方法。利用模板首先合成介孔纳米二氧化硅微球,再用水热反应法,成功制备了非功能化和巯基、氨基功能化中空纳米二氧化硅微球。利用透射电子显微镜,热重分析等手段对其形貌进行了表征。另外,对中空介孔纳米二氧化硅微球的形成机制进行了探讨。     

纳米级二氧化硅微球在三聚氰胺甲醛树脂上的微米化组装包覆

通过溶胶-凝胶法制得平均粒径为226 nm形状规整的球形二氧化硅微球.用硅烷偶联剂KH-570作表面处理后,使用十二烷基硫酸钠作为乳化剂,采用超声化学的方法,将纳米级二氧化硅组装包覆在三聚氰胺甲醛树脂表面,形成具有高比表面积的微米级颗粒.通过红外光谱FT-IR、扫描电子显微镜、激光粒度测试等方法对二氧化硅及组装颗粒进行表征,并对合成机理进行分析.发现二氧化硅在三聚氰胺甲醛树脂颗粒上均匀包覆,最后包覆物粒径分布较均一,平均粒径为30 μm.     

利用聚合物乳液合成聚甲基丙烯酸甲酯/二氧化硅纳米杂化材料

通过正硅酸乙酯分别在聚甲基丙烯酸甲酯乳液和四氢呋喃溶液中的溶胶－凝胶反应制备出不同的聚甲基丙烯酸甲酯／二氧化硅复合材料。利用扫描电镜、透镜电镜、差热分析和热失重对试样进行了分析。结果表明，利用聚合物乳液可以获得纳米分散的聚甲基丙烯酸甲酯／二氧化硅复合材料，并且在某种程度上其分散尺度小于利用聚合物溶液获得的复合材料。同时，利用聚合物乳液来制备聚甲基丙烯酸甲酯／二氧化硅杂化材料更有利于凝胶过程中二氧化硅网络的形成。     

纳米级二氧化硅微球在密胺树脂上的微米化组装包覆

通过溶胶-凝胶法制得平均粒径为226 nm形状规整的球形二氧化硅微球。 用硅烷偶联剂KH-570作表面处理后,使用十二烷基硫酸钠作为乳化剂,采用超声化学的方法,将纳米级二氧化硅组装包覆在三聚氰胺甲醛树脂表面,形成具有高比表面积的微米级颗粒。 通过红外光谱FT-IR、扫描电子显微镜、激光粒度测试等方法对二氧化硅及组装颗粒进行表征,并对合成机理进行分析。发现二氧化硅在三聚氰胺甲醛树脂颗粒上均匀包覆,最后包覆物粒径分布较均一,平均粒径为30 μm。     

Microporous Silica Hollow Nanospheres Templated by Anionic Polypeptide

Anionic polypeptide, the poly(sodium L-glutamate), was applied to fabricate microporous silica hollow nanospheres templated by the secondary structures of the polypeptide as porogens. In the synthesis, 3-aminopropyltrimethoxysilane (APMS) and tetraethyl orthosilicate (TEOS) were used as the silica sources, and the coassembly followed the mechanism of the anionic surfactant-templated mesoporous silica (AMS) through a S_-N₊-I_- pathway, where S indicates the anionic polypeptide, I indicates inorganic precursors (TEOS), and N indicates costructure-directing agent (APMS), which interacted with the negatively charged anionic polypeptide secondary structures electrostatically and cocondensed with silica source to form the silica framework. The product was subjected to characterizations of X-ray diffraction (XRD), infrared (IR) spectroscopy, thermogravimetric (TG) analysis, scanning electron microscopy (SEM), transmitted electron microscopy (TEM), and nitrogen adsorption-desorption measurement. It was found that the pH value of the synthesis solution was an important factor to the morphological control of the silica products. Besides the microporous hollow nanospheres, microporous submicron silica solid and hollow spheres were also obtained facilely by changing the synthesis parameters. Our study further implied that anionic polypeptides, which were able to control mineralization of calcium carbonate and calcium phosphate, could also induce silica condensation in the presence of proper silica precursors. It was also expected that functional calcium carbonate (phosphate)/silica-nanocomposite materials would be fabricated under the control of the anionic polypeptide.     

Synthesis of Silica Hollow Spheres with Diameter Around 50 nm by Anionic Surfactant

Silica hollow spheres(SHSs) have attracted great attention because of their low toxicity,low density,large surface area,high chemical and thermal stability,and surface permeability.They can be widely applied in storage[1],catalysis[2],drug delivery[3,4],low-dielectric-constant materials[5],low-refractive materials[6-8],and so on.Up to now,there have been various methods to produce SHSs.Inorganic[9] or organic particles[10],such as polystyrene or calcium carbonate,were used as hard templates to create hollow cavities.However,the multistep synthetic process and the lack of structural robustness of the shells upon template removal process weaken their application.Soft templates,including oil-in-water emulsions[1],[2],vesicles[13],micelle[14,15] and gas bubbles[16],are applied widely.     

中空纤维担载氧化硅膜的制备及结构研究

采用SXRD,HRTEM,FTIR,SEM和氮气吸附等测试手段对膜结构、形貌、孔径及其分布进行了表征.SXRD和HRTEM结果显示,所制备的膜具有短程有序结构.SEM分析发现膜表面完整.气体渗透实验表明,担载膜具有一定的气体选择性,在0.1MPa下对H₂/N₂和CH₄/N₂的分离因子分别为2.25和1.56,气体透过膜孔的扩散由努森机制所控制.等温氮气吸附实验显示,经500℃热处理后氧化硅膜的最可几孔径小于3.34nm,非担载膜的比表面积为919.8m²/g,孔容为0.43mL/g.     

Preparation of Hydrophilic UHMWPE Hollow Fiber Membranes by Chemically Bounding Silica Nanoparticles

In this work, ultra-high molecular weight polyethylene (UHMWPE) microfiltration hollow fiber membranes prepared via the thermally induced phase separation (TIPS) method were modified by chemically bounding hydrophilic silica (SiO_2) nanoparticles onto the surface to improve anti-fouling performance. A range of testing techniques including attenuated total reflection Flourier transformed infrared spectroscopy(ATR-FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), water contact angle, mechanical test,filtration and anti-fouling performance were carried out to discuss the influence of different modification conditions on the properties of the membranes. The prepared hollow fiber membranes display the significantly excellent performance when the vinyl trimethoxy silane (VTMS) concentration was 13%, the pH value of the hydrolyzate was 4 and the hydrolysis reaction time was 6 h. In particular, the hydrophilicity of modified membranes was improved effectively, resulting in the enhancement of membrane anti-fouling properties. The results of this work can be consulted for improving the anti-fouling performance of the UHMWPE microfiltration hollow fiber membrane applied in the field of water purification.     

Chirality Transfer in the Formation of Poly(oxymethylene) Helices by Anionic Polymerization

In this article, we present the synthesis of a series of oligo(oxymethylenes) capped with 1‐phenylethanol and MeOH. The anionic condition affords enantiomerically pure oligo(oxymethylene) oligomers, while the cationic oligomerization leads to a racemic mixture of the oligo(oxymethylene) chain.     

以橡子为碳源制备的空心磁性碳纳米球及其吸附性能

以橡子为碳源,通过高温煅烧法制备了粒径均匀的磁性空心碳纳米球(MHCNS)。经过HCl浸泡处理可得MHCNS-1,再经HNO_3和NH_3·H_2O处理得MHCNS-2。MHCNS-2粒径均匀,直径为20～40 nm,球壁厚度为3～5 nm。MHCNS-2的尺寸可通过改变镍离子与氢氧化钾的添加量和比例进行调控。通过X射线粉末衍射、扫描电镜、透射电镜、振动样品磁强计等方法对制备的产物进行了表征,进而分析了其生长机制。MHCNS-2对于有机染料亚甲基蓝(MB)的吸附性能的实验结果表明,MHCNS-2具有强吸附性能,当MB溶液浓度为100 mg·L~(-1)时,吸附量可以达到185 mg·g~(-1)。MHCNS对布洛芬的载药释药实验结果表明,MHCNS-2载药率可达44%,释药率达70%,有着良好的载药与释药能力。     

Preparation of Hollow Silica Microspheres via Poly(N-isopropylacrylamide)

Core-shell structured SiO₂/poly(N-isopropylacrylamide) (SiO₂/PNIPAM) microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl or-thosilicate (TEOS) on the surface of PNIPAM template at 50 oC. The PNIPAM template can be easily removed by water at room temperature so that SiO₂ hollow microspheres were finally obtained. The transmission electron microscope and scanning electron microscope observations indicated that SiO₂ hollow microspheres with an average diameter of 150 nm can be formed only if there are enough concentration of PNIPAM and TEOS, and the hy-drolysis time of TEOS. FTIR analysis showed that part of PNIPAM remained on the wall of SiO₂ because of the strong interaction between PNIPAM and silica. This work provides a clean and efficient way to prepare hollow microspheres.     

Recent Advances in the Synthesis,Surface Modifications and Applications of Core‐Shell Magnetic Mesoporous Silica Nanospheres

The hierarchically structured core‐shell magnetic mesoporous silica nanospheres (Mag‐MSNs) have attracted extensive attention, particularly in studies involving reliable preparations and diverse applications of the multifunctional nanomaterials in multi‐disciplinary fields. Intriguingly, Mag‐MSNs have been prepared with well‐designed synthesis strategies and used as adsorbent materials, biomedicines, and in proteomics and catalysis due to their excellent magnetic responsiveness, enormous specific surface area and readiness for surface modifications. Through a carefully designed surface modification of Mag‐MSNs, the performance and application prospects of the material are greatly improved. Typically, the introduction of various molecular matrices into the shell of Mag‐MSNs facilitates the combination of surface modifications and magnetic separation technology. So far, as sustainable chemistry is concerned, it is important to recover the functionalized core‐shell Mag‐MSNs after the reaction and reuse them without losing activity. In this review, the design conceptions and the construction of core‐shell Mag‐MSNs are discussed. Furthermore, various surface modification approaches of core‐shell Mag‐MSNs are summarized, and recent applications of these functionalized nanomaterials in the fields of biomedicine, catalysis, proteomics and wastewater treatment are exemplified.