Preparation of Helical Mesoporous Ethenylene-silica Nanofibers with Lamellar Mesopores on Their Surface

The morphologies and pore architectures of mesoporous ethenylene‐silica were controlled using cetyltrimethylammonium bromide (CTAB) as template and (S)‐β‐citronellol as a co‐structure‐directing agent under basic conditions. When the (S)‐β‐citronellol/CTAB molar ratios are in the range of 0.75–2.0, helical nanofibers were obtained. With increasing the (S)‐β‐citronellol/CTAB molar ratio, the lengths of the nanofibers increases. Lamellar mesopores were identified on the surfaces of the nanofibers prepared in the (S)‐β‐citronellol/CTAB molar ratio range of 1.5–2.0. At the (S)‐β‐citronellol/CTAB molar ratio of 2.5:1, nanoparticles with nanoflakes on the surfaces were obtained. The field emission scanning electron microscopy images taken after different reaction times indicated that the helical pitches of the nanofibers decreased with increasing the reaction time. Helical 1,4‐phenylene‐silica and methylene‐silica nanofibers were also prepared. The results indicated that the morphologies and pore architectures of the obtained organic‐inorganic hybrid silicas are also sensitive to the hybrid silica precursors. Helical ethenylene‐silica nanofibers with lamellar mesopores on their surfaces can be also prepared using the mixtures of CTAB and racemic citronellol within a narrower citronellol/CTAB molar ratio range.     

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.     

Preparation of Hierarchical Mesoporous Silica Nanoparticles through a Single‐Templating Approach

Silicas with hierarchical porous architectures attracted much attention, due to their potential applications in catalysis and separation. Generally, they were prepared through dual‐ or triple‐templating approaches. Herein, mesoporous silica nanoparticles with rod‐like pore channels inside and lamellar mesopores on the surfaces were prepared using the self‐assemblies of a chiral low‐molecular‐weight amphiphile as templates through a single‐templating approach. The formation of the lamellar mesopores was studied by taking field‐emission scanning electron microscopy and transmission electron microscopy images after different reaction times. The lamellar pores were proposed to be formed by merging rod‐like micelles during the sol‐gel process. Moreover, helical nanofibers with rod‐like pore channels inside and lamellar mesopores on the surfaces were prepared with the addition of n‐octanol as a co‐structure‐directing agent.     

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 Multilayered 1,2-Ethylene-silica Nanotubes Through a Dual-templating Approach

Multilayered 1,2-ethylene-silica nanotubes were prepared with cetyltrimethylammonium bromide(CTAB)as a template and(S)-β-citronellol(CN)as a co-structure-directing agent.For a better understanding of t...     

Mesoporous silicas by self-assembly of lipid molecules: ribbon, hollow sphere, and chiral materials

Using lipids (N-acyl amino acids) and 3-aminopropyltriethoxysilane as structure- and co-structure-directing agents, mesoporous silicas with four different morphologies, that is, helical ribbon (HR), hollow sphere, circular disk, and helical hexagonal rod, were synthesized just by changing the synthesis temperature from 0 degrees C to 10, 15, or 20 degrees C. The structures were studied by electron microscopy. It was found that 1) the structures have double-layer disordered mesopores in the HR, radially oriented mesopores in the hollow sphere, and highly ordered straight and chiral 2D-hexagonal mesopores in the disklike structure and helical rod, respectively; 2) these four types of mesoporous silica were transformed from the flat bilayered lipid ribbon with a chain-interdigitated layer phase through a solid-solid transformation for HR formation and a dissolving procedure transformation for the synthesis of the hollow sphere, circular disk, and twisted morphologies; 3) the mesoporous silica helical ribbon was exclusively right-handed and the 2D-hexagonal chiral mesoporous silica was excessively left-handed when the L-form N-acyl amino acid was used as the lipid template; 4) the HR was formed only by the chiral lipid molecules, whereas the 2D-hexagonal chiral mesoporous silicas were formed by chiral, achiral, and racemic lipids. Our findings give important information for the understanding of the formation of chiral materials at the molecular level and will facilitate a more efficient and systematic approach to the generation of rationalized chiral libraries.     

以EDTANa2为矿化剂近中性条件下室温合成介孔二氧化硅

利用EDTANa2作为矿化剂, 在近中性条件下于室温合成了厚壁(约3 nm)蠕虫介孔分子筛. 在反应物配比为n(CTAB):n(TEOS):n(EDTANa2):n(H2O)=(0.05~0.2):(0.1~2):(0.1~0.5):(100~500)范围内都能得到介孔二氧化硅. 以XRD、N2吸附、FTIR、SEM和TEM详细考察了体系配比和温度对介孔二氧化硅结构和形貌的影响, 发现CTAB用量越大, 介孔d值相应增大. 温度对介孔二氧化硅的结构和形貌有很大的影响, 温度在2~15 ℃范围内都能生成孔径分布较规则的介孔, 介孔材料的形貌随温度的升高由空心管变成小颗粒聚集体; 合成的介孔分子筛中的模板剂可以通过乙醇萃取的方式除去. 提出了介孔的生成遵从(S+-E-)0-I0中性模板机理.     

Synthesis of highly-ordered mesoporous silica particles using mixed cationic and anionic surfactants as templates

We applied a molecular assembly formed in an aqueous surfactant mixture of cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium octylsulfate (SOS) as templates of mesoporous silica materials. The hexagonal pore size can be controlled between 3.22 and 3.66 nm with the mixed surfactant system. In addition, we could observe the lamellar structure of the mixed surfactants with precursor molecules, which strongly shows the possibility of precise control of both the pore size and the structure of pores by changing the mixing ratio of surfactants. Moreover, use of the cationic surfactant having longer hydrophobic chain like stearyltrimethylammonium bromide (STAB) caused the increase in d(100) space and shifted the point of phase transition from hexagonal phase to lamellar phase to lower concentration of SOS.     

Mesoporous nanotubes of iron phosphate: synthesis, characterization, and catalytic property

Iron phosphate nanotubes with mesoporous walls are solvothermally synthesized using sodium dodecyl sulfate (SDS) as a template. With different template concentrations, various shapes of nanosized iron phosphates can be obtained. When the concentration of SDS is set at the transition regions between the lamellar and the hexagonal mesophases, according to its phase diagram, the coassembly of iron phosphate precursor and SDS forms a flake-type mesoporous iron phosphate. Otherwise, nanoparticles or bulky sheets of iron phosphates are obtained. The followed solvothermal treatments on the mesoporous iron phosphate flakes produce iron phosphate nanotubes with mesoporous walls. The removal of the surfactant by acetate exchange and heat treatment results in the clean mesoporous nanotubes of iron phosphate with diameters of 50-400 nm and lengths of several microns. The nanotubular and mesoporous iron phosphate possesses a specific surface area of 232 m2/g and a bimodal distribution of pore sizes, corresponding to the size of mesopores in the walls and the diameter of the nanotubes, respectively. The novel nanotubular iron phosphate with composite meso-macroporous structure, in favor of the diffusion of reactive molecules, has been tested for direct hydroxylation of benzene with hydrogen peroxide and has shown better catalytic performance compared with the conventional particulate mesoporous iron phosphate.     

Fabrication of MCM-41 mesoporous silica through the self-assembly supermolecule of β-CD and CTAB

Using the self-assembly β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTAB) as structure-directing agents, high-quality ordered MCM-41 silicas have been prepared. Small-angle X-ray diffraction (SXRD), N₂ adsorption-desorption and scanning electron microscope (SEM) techniques were used to characterize the calcined samples. Results showed that the pore structure of the resulting mesoporous silica belonged to the two-dimensional hexagonal structure (space group p6mm). The high-quality hexagonal structure was formed as n?1 (n denotes molar ratio of β-CD to CTAB). N₂ adsorption-desorption curves revealed type IV isotherms, H4 hysteresis loops, for all samples, and H1 hysteresis loops for samples at n=0, 0.1, 1 and 2, respectively. The pore size and the pore wall thickness of the samples increased with the increase in n values, respectively.     

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc.     

Detailed Structural Characterizations of SBA‐15 and MCM‐41 Mesoporous Silicas on a High‐Resolution Transmission Electron Microscope

Using high‐resolution transmission electronic micrograph (HR‐TEM) observation, one can clearly see the pore geometry of the MCM‐41 and SBA‐15 mesoporous silicas to determine that their pore shapes are hexagonal and round, respectively. With the perpendicular orientations of the nanochannels to the electron beam, parallel line images of the (100) and (110) repeating spacings were observed. In the SBA‐15 mesoporous silicas, there are byproducts of the granular silica and disordered mesostructures, attributed to the weak hydrogen interactions between Pluronic 123 blockcopolymer and the silica species. There are also many different and significant +π disclination defects in SBA‐15 and MCM‐41 surfactant‐silica composites. The SBA‐15 with a thicker silica wall is more stable under irradiation by high‐energy electron beams compared to MCM‐41, which has thinner wall thickness. Some carbon nanostructure impurities were found in some carbon films on the metal grids.     

Ordered nanostructures from self‐assembly of H‐shaped coil–rod–coil molecules

A new class of π‐conjugated, skewed H‐shaped oligomers, consisting of biphenyl, phenylene vinylene, and phenylene ethynylene units as the rigid segment, were synthesized via Sonogashira coupling and Wittig reactions. The coil segments of these molecules were composed of poly(ethylene oxide) (PEO) or PEO with lateral methyl groups between the rod and coil segment, respectively. The experimental results revealed that the lateral methyl groups attached to the surface of the rod and coil segments dramatically influenced the self‐assembling behavior of the molecules in the crystalline phase. H‐shaped rod–coil molecules containing a lateral methyl group at the surface of the rod and PEO coil segments self‐assemble into a two‐dimensional columnar or a three‐dimensional body‐centered tetragonal nanostructures in the crystalline phase, whereas molecules lacking a lateral methyl group based on the PEO coil chain self‐organize into lamellar or hexagonal perforated lamellar nanostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 85–92     

Post-treatment and characterization of novel luminescent hybrid bimodal mesoporous silicas

A novel luminescent hybrid bimodal mesoporous silicas (LHBMS) were synthesized via grafting 1,8-Naphthalic anhydride into the pore channels of bimodal mesoporous silicas (BMMs) for the first time. The resulting samples were characterized by powder X-ray diffraction (XRD), N₂ adsorption/desorption measurement, Fourier transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM), UV-vis absorption spectroscopy, and Photoluminescence spectroscopy (PL). The results show that 1,8-Naphthalic anhydride organic groups have been successfully introduced into the mesopores of the BMMs and the hybrid silicas are of bimodal mesoporous structure with the ordered small mesopores of around 3 nm and the large mesopores of uniform intra-nanoparticle. The excellent photoluminescent performance of LHBMS has a blue shift compared to that of 2-[3-(triethoxysilyl) propyl-1 H-Benz [de]isoquinoline-1, 3(2 H)-dione, suggesting the existence of the quantum confinement effectiveness.     

Cubic Mesoporous Titanium Phosphonates with Multifunctionality

Cubic mesoporous titanium phosphonate materials with bridged organic groups inside the framework were synthesized by means of a one‐pot hydrothermal autoclaving process, with the assistance of cationic surfactant cetyltrimethylammonium bromide. 1‐Hydroxyethylidene‐1,1‐diphosphonic acid was used as the coupling molecule. A typical cubic mesophase with surface area of 1052 m² g^?1 and pore size of 2.6 nm was confirmed by XRD, TEM, and N₂ sorption analysis. The organophosphonate groups were homogeneously incorporated in the network of the mesoporous solids, as revealed by FTIR and magic‐angle spinning (MAS) NMR spectroscopy, and thermogravimetry and differential scanning calorimetry (TG‐DSC) measurements. The synthesized hydroxyethylidene‐bridged cubic mesoporous titanium phosphonates proved to be thermally stable up to 350 °C, with a well‐preserved hybrid framework and cubic mesoporous architecture. The obtained cubic mesophase could be transformed into a hexagonal mesophase by simply adjusting the molar ratios of the added raw materials, namely, a Ti/P molar ratio of 1:4 and a CTAB/Ti molar ratio of 1.9–2.3 for the cubic phase and Ti/P molar ratio of 3:4 and CTAB/Ti molar ratio of 0.1–0.4 for the hexagonal phase. The cubic hybrid materials could be used as efficient photocatalysts for the photodegradation of rhodamine B. Moreover, they were also used for adsorption of CO₂ and heavy metal ions and exhibited a significant capture amount of around 1.0 mmol g^?1 for CO₂ molecules at 35 °C and high adsorption capacity of 28.5 μmol g^?1 for Cu²⁺ ions with good reusability, which demonstrated their promising potential in environmental remediation.     

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     

层状和MSU结构的介孔纳米二氧化锆

在不添加任何结构稳定剂的条件下, 首次用固态反应结构导向法成功地合成了具有层状结构和MSU结构的介孔纳米二氧化锆. 研究发现, 通过有效地控制晶化条件, 二氧化锆的晶相、比表面和孔结构可以方便地得以调变. 晶相的转变由粒度大小控制, 并且构成无机骨架的相态不同, 合成样品的热稳定性存在差异. 结果显示, 介孔纳米二氧化锆的形成仍遵循超分子液晶模板机制, 且由碱锆摩尔比的大小控制介观相的转化, 低碱锆摩尔比条件下形成层状相, 而高碱锆摩尔比条件下为维持整个体系的低能稳定状态, 在电荷作用下形成反棒状胶束结构.     

Assessment of ordered and complementary pore volumes in polymer-templated mesoporous silicas and organosilicas

A method to determine the volumes of ordered mesopores and complementary small pores in polymer-templated ordered mesoporous silicas and organosilicas is proposed on the basis of the existing relation between the pore width and unit cell values obtained by the XRD structure modeling and the adsorption pore volume.     

多面体倍半硅氧烷制备有序介孔氧化硅材料

Octa(tetramethylammonium)-polyhedral oligomeric silsesquioxane(TMA-POSS) with cage-like structure was synthesized, the structure was characterized by NMR, FTIR and Elemental analyses. The mesoporous silica was prepared under alkaline condition using TMA-POSS as the silicon source and hexadecyltrimethylammonium bromide (CTAB) as the template, the structures of these products were characterized by XRD, TEM and nitrogen adsorption and desorption methods. The results indicate that the synthesized silica exhibites a well-ordered hexagonal pore structure with larger specific surface area. With increasing of CTAB molar ratio, the spacing of the crystal plane d100 is increased. The effects of the pH values on the mesoporous structure in the reaction system with different molar ratio of nPOSS / nCTAB were investigated. The synthesis mechanism of mesoporous silica was also discussed.     

孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料的制备及其高光催化活性

本文报道一种孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料的制备.该介孔材料是以两维六方有序结构、直孔道、锐钛矿70TiO2-30SiO2-950纳米复合介孔材料(于950oC晶化2 h)为前驱体, NaOH为SiO2的刻蚀剂,通过“在孔壁内造孔”的方法获得.我们的策略是采用温和的造孔条件,如稀NaOH溶液,合适的温度与固/液比等.采用X射线衍射(XRD),透射电镜(TEM)和低温N2吸附等技术对样品的介孔结构进行了系统表征.结果表明,墙内孔的密度非常高,孔径均一(平均尺寸3.6 nm),且在三维网络高度连通原孔道,但介孔结构仍保持其完整性.锐钛矿纳米晶粒的结晶度和大小在墙内造孔前后基本保持不变.该材料光催化降解罗丹明B(0.303 min–1)与亚甲基蓝(0.757 min–1)的活性相当高,此活性分别是其母体材料的5.1和5.3倍,甚至是Degussa P25光催化剂的16.5和24.1倍.这充分表明三维连通孔道结构对活性的大幅提高起了关键作用.孔道三维连通式锐钛矿TiO2-SiO2纳米复合介孔材料对上述污染物展现出意想不到的高降解活性,显著高于迄今已报道的金属氧化物基介孔材料对上述污染物的降解活性.更重要的是,该光催化剂具有相当高的稳定性和重复使用性.相信,本方法将为具有超高性能的孔道三维相互连通其它金属氧化物基介孔材料的制备铺平了道路.
　　小角XRD结果表明,母体材料的孔道是两维六方有序结构,在孔壁内造孔之后,样品原有的介孔结构仍保持其规整性.宽角XRD结果显示,二氧化钛的晶相是锐钛矿,晶粒尺寸为10.8 nm.造新孔之后,锐钛矿纳米晶粒的结晶度和大小与母体样品的相比变化不大. TEM结果显示,母体样品的孔壁内没有孔.孔道是两维六方有序排列的直孔道,孔径大小均一(平均尺寸4.1 nm).高分辨透射电镜(TEM)观察揭示,锐钛矿纳米晶粒(平均大小11.3 nm)在孔壁内随机排列,并与无定形SiO2纳米颗粒相互连接,相间共存,形成类似“砖块?水泥砂浆”砌成的孔壁,这种独特的复合骨架结构赋予其很高的稳定性.当一些SiO2纳米颗粒被去除之后, TEM观察显示,孔壁内有密集分布的孔,这些孔取向随机,并在三维方向连通原孔道,但介孔骨架结构仍保持其完整性.墙内孔的大小范围很窄(3.1?4.3 nm),平均大小为3.6 nm.高分辨TEM观察显示,锐钛矿晶粒大小与母体材料内的相比基本未变.上述结果与XRD结果一致.低温N2吸附表征结果显示,母体样品内只有一种孔道,孔径为4.0 nm.去除部分SiO2后的样品内有两种孔道,孔径分别是3.4和4.1 nm.这些结果与TEM的观察吻合.罗丹明B与亚甲基蓝在造孔前后样品内扩散速率评价结果显示,其在三维连通孔道内的扩散速率很高,大约是其母体材料内的5倍以上.这表明相互连通的孔道网络结构非常有利于客体分子在其内扩散.光催化降解性能评价结果显示,罗丹明B与亚甲基蓝在相互连通孔道内降解的速率相当高,分别是其在不连通孔道内的5.1和5.3倍.这充分证明孔道三维相互连通对活性的大幅提高起了关键作用.我们对材料的稳定性和重复使用性作了评价,经过10次循环使用孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料,其吸附与光催化降解罗丹明B的性能变化不大.这充分证明本文制备的孔道连通复合介孔材料的性能是相当稳定的和可重复使用的.该方法可用于制备具有超高性能的孔道三维相互连通其它金属氧化物基介孔材料,如Nb2O5, Ta2O5等.