Synthesis of ordered mesoporous crystalline carbon-anatase composites with high titania contents

A direct-triblock-copolymer templating method is demonstrated to synthesize ordered mesoporous crystalline C-TiO(2) (MCT) composites using phenolic resins and acid-base pairs [acidic TiCl(4) and basic counterpart Ti(OC(4)H(7))(4)] as carbon and titanium sources, respectively. The composites possess highly crystalline anatase pore walls that are "glued" by amorphous carbon, ordered mesostructure, high surface areas (approximately 200 m(2)/g), and large pore volumes (approximately 0.15 cm(3)/g). The titania content is as high as 87 wt%. MCT composite favors the immobilization of proteins and enhances the electrocatalytic properties in relation to the reduction of hydrogen peroxide.     

Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas

Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.     

Synthesis of highly ordered mesoporous crystalline WS(2) and MoS(2) via a high-temperature reductive sulfuration route

A high-temperature reductive sulfuration method is demonstrated to synthesize highly ordered mesoporous metal sulfide crystallites by using mesoporous silica as hard templates. H2S gas is utilized as a sulfuration agent to in situ convert phosphotungstic acid H3PW12O40.6H2O to hexagonal WS2 crystallites in the silica nanochannels at 600 degrees C. Upon etching silica, mesoporous, layered WS2 nanocrystal arrays are produced with a yield as high as 96 wt %. XRD, nitrogen sorption, SEM, and TEM results reveal that the WS2 products replicated from the mesoporous silica SBA-15 hard template possess highly ordered hexagonal mesostructure (space group, p6mm) and rodlike morphology, analogous to the mother template. The S-W-S trilayers of the WS2 nanocrystals are partially oriented, parallel to the mesochannels of the SBA-15 template. This orientation is related with the reduction of the high-energy layer edges in layered metal dichalcogenides and the confinement in anisotropic nanochannels. The mesostructure can be 3-D cubic bicontinuous if KIT-6 (Iad) is used as a hard template. Mesoporous WS2 replicas have large surface areas (105-120 m2/g), pore volumes ( approximately 0.20 cm3/g), and narrow pore size distributions ( approximately 4.8 nm). By one-step nanocasting with the H3PMo12O40.6H2O (PMA) precursor into the mesochannels of SBA-15 or KIT-6 hard template, highly ordered mesoporous MoS2 layered crystallites with the 2-D hexagonal (p6mm) and 3-D bicontinuous cubic (Iad) structures can also be prepared via this high-temperature reductive sulfuration route. When the loading amount of PMA precursor is low, multiwalled MoS2 nanotubes with 5-7 nm in diameter can be obtained. The high-temperature reductive sulfuration method is a general strategy and can be extended to synthesize mesoporous CdS crystals and other metal sulfides.     

Solvent evaporation induced aggregating assembly approach to three-dimensional ordered mesoporous silica with ultralarge accessible mesopores

A solvent evaporation induced aggregating assembly (EIAA) method has been demonstrated for synthesis of highly ordered mesoporous silicas (OMS) in the acidic tetrahydrofuran (THF)/H(2)O mixture by using poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA) as the template and tetraethylorthosilicate (TEOS) as the silica precursor. During the continuous evaporation of THF (a good solvent for PEO-b-PMMA) from the reaction solution, the template molecules, together with silicate oligomers, were driven to form composite micelles in the homogeneous solution and further assemble into large particles with ordered mesostructure. The obtained ordered mesoporous silicas possess a unique crystal-like morphology with a face centered cubic (fcc) mesostructure, large pore size up to 37.0 nm, large window size (8.7 nm), high BET surface area (508 m(2)/g), and large pore volume (1.46 cm(3)/g). Because of the large accessible mesopores, uniform gold nanoparticles (ca. 4.0 nm) can be introduced into mesopores of the OMS materials using the in situ reduction method. The obtained Au/OMS materials were successfully applied to fast catalytic reduction of 4-nitrophenol in the presence of NaHB(4) as the reductant. The supported catalysts can be reused for catalytic reactions without significant decrease in catalysis performance even after 10 cycles.     

Facile synthesis for ordered mesoporous gamma-aluminas with high thermal stability

The facile synthesis of highly ordered mesoporous aluminas with high thermal stability and tunable pore sizes is systematically investigated. The general synthesis strategy is based on a sol-gel process associated with nonionic block copolymer as templates in ethanol solvent. Small-angle XRD, TEM, and nitrogen adsorption and desorption results show that these mesoporous aluminas possess a highly ordered 2D hexagonal mesostructure, which is resistant to high temperature up to 1000 degrees C. Ordered mesoporous structures with tunable pore sizes are obtained with various precursors, different acids as pH adjustors, and different block copolymers as templates. These mesoporous aluminas have large surface areas (ca. 400 m2/g), pore volumes (ca. 0.70 cm3/g), and narrow pore-size distributions. The influence of the complexation ability of anions and hydro-carboxylic acid, acid volatility, and other important synthesis conditions are discussed in detail. Utilizing this simple strategy, we also obtained partly ordered mesoporous alumina with hydrous aluminum nitrate as the precursor. FTIR pyridine adsorption measurements indicate that a large amount of Lewis acid sites exist in these mesoporous aluminas. These materials are expected to be good candidates in catalysis due to the uniform pore structures, large surface areas, tunable pore sizes, and large amounts of surface Lewis acid sites. Loaded with ruthenium, the representative mesoporous alumina exhibits reactant size selectivity in hydrogenation of acetone, D-glucose, and D-(+)-cellobiose as a test reaction, indicating the potential applications in shape-selective catalysis.     

Co-hydrolysis and Seed-Induced Synthesis of Basic Mesoporous ZSM-5 Zeolites with Enhanced Catalytic Performance

For zeolite catalysts, the regulation of active site and pore structure plays an important role in the enhancement of their catalytic performance. In this work, a one-pot and organic template-free co-regulation route is proposed to straightforwardly synthesize basic mesoporous ZSM-5 zeolites with adjustable alkaline-earth metal species. The synthesis pathway combines two decisive strategies: 1) the seed-induced interface assembly growth method and 2) the acidic co-hydrolysis/condensation of aluminosilicate species and alkaline-earth metal (e.g., Mg, Ca, Sr, or Ba) sources. It is interesting that the mesoporous structure was self-evolved through particle-attached seed-interfacial crystallization without the assistance of any template. Meanwhile, the incorporation of alkaline-earth metals species is homogeneous and highly dispersed in the solid products during the whole crystallization process, and finally generate the superior basicity. Catalysis tests of the as-synthesized samples displayed their novel performance in the typical base reaction of Knoevenagel condensation, even for bulky substrates owing to the enhanced diffusion arising from the meso/microporous network. This finding opens new possibilities for facile, cost-effective, and environmentally friendly synthesis of mesoporous high-silica zeolites with tunable acid/base properties, and deepens our understanding of the particle-attached crystallization.     

Self-assembling and size-selective synthesis of Ni and NiO nanoparticles embedded in ordered mesoporous carbon and polymer frameworks

We demonstrate the self-assembling and size-selective synthesis of uniform and highly dispersed Ni or NiO nanoparticles with diameters below 12 nm embedded in ordered mesoporous carbon or polymer frameworks. Self-assembly is induced by evaporation of the solvent from a mixture of metal-containing liquid crystalline (LC) mesophases of triblock copolymer and transition metal nitrate hydrate, and the carbon source is low-polymerized phenolic resol. Characterization by XRD, N(2) sorption isotherms, TEM, HRSEM, ICP-AES, TG, and XPS techniques has indicated an ordered 2D hexagonal mesostructure, high surface areas between 524 and 721 m(2) g(-1), uniform pore sizes of about 4.0 nm, large pore volumes ranging from 0.34 to 0.58 cm(3) g(-1), and metal contents ranging from 0.6 to 10.0 wt%. There is a high degree of dispersion, and a small size of nanoparticles throughout the whole framework, without aggregation outside of the pores due to the confinement effect of the mesoporous ordered matrix. The mesoporous solids show excellent adsorption properties for dyes and permit an easy magnetic separation procedure. This method is expected to be applicable to other mesoporous transition metal(oxide)-containing carbon catalysts.     

Large-pore mesoporous SBA-15 silica particles with submicrometer size as stationary phases for high-speed CEC separation

A new mesoporous sphere-like SBA-15 silica was synthesized and evaluated in terms of its suitability as stationary phases for CEC. The unique and attractive properties of the silica particle are its submicrometer particle size of 400 nm and highly ordered cylindrical mesopores with uniform pore size of 12 nm running along the same direction. The bare silica particles with submicrometer size have been successfully employed for the normal-phase electrochromatographic separation of polar compounds with high efficiency (e.g., 210,000 for thiourea), which is matched well with its submicrometer particle size. The Van Deemeter plot showed the hindrance to mass transfer because of the existence of pore structure. The lowest plate height of 2.0 microm was obtained at the linear velocity of 1.1 mm/s. On the other hand, because of the relatively high linear velocity (e.g., 4.0 mm/s) can be generated, high-speed separation of neutral compounds, anilines, and basic pharmaceuticals in CEC with C18-modified SBA-15 silica as stationary phases was achieved within 36, 60, and 34 s, respectively.     

双酸体系下有序介孔SO42-/ZrO2-SiO2材料的合成

采用一锅合成法通过调变自组装过程中硫酸和盐酸的体积比,成功制备了系列介孔SO₄^2-/ZrO₂-SiO₂固体酸材料(Zr/Si物质的量为1.1).XRD、UV-Vis DRS、HR-TEM等表征结果表明,所得材料均具有高度有序的二维介孔结构及四方相氧化锆的晶体结构.氮吸附和FT-IR表征结果进一步发现,通过改变硫酸/盐酸体积比可有效调变材料比表面积、孔容、孔径及表面L酸与B酸的相对强度.与纯硅介孔分子筛SBA-15不同,此系列SO₄^2-/ZrO₂-SiO₂固体酸材料均在正戊烷的异构化反应中表现出较高的催化活性和稳定性.其原因在于,在合成过程中硫酸的加入不仅促使了酸基的形成,而且稳定了催化剂的晶体结构;盐酸的存在则保持了有序的介孔结构.由此可见,混酸合成体系有望制备出结构有序、酸性可调、催化性能优越的新型催化材料,并在众多酸催化反应中取得应用.     

介孔分子筛SBA-15作为高效液相色谱固定相分离维生素E

以三嵌段共聚物P123聚环氧乙烷-聚环氧丙烷-聚环氧乙烷(PEO-PPO-PEO)为模板,在强酸性(1.6mol/L HCl)条件下,水热合成了棒状二维六方有序介孔材料SBA-15.粒径棒长约1～1.5μm,直径为400～500nm,平均孔径5.8nm,BET比表面积799㎡/g.并用合成的SBA-15作为正相高效液相...     

Free-standing mesoporous carbon thin films with highly ordered pore architectures for nanodevices

We report for the first time the synthesis of free-standing mesoporous carbon films with highly ordered pore architecture by a simple coating-etching approach, which have an intact morphology with variable sizes as large as several square centimeters and a controllable thickness of 90 nm to ～3 μm. The mesoporous carbon films were first synthesized by coating a resol precursors/Pluronic copolymer solution on a preoxidized silicon wafer and forming highly ordered polymeric mesostructures based on organic-organic self-assembly, followed by carbonizing at 600 °C and finally etching of the native oxide layer between the carbon film and the silicon substrate. The mesostructure of this free-standing carbon film is confirmed to be an ordered face-centered orthorhombic Fmmm structure, distorted from the (110) oriented body-centered cubic Im3?m symmetry. The mesoporosity of the carbon films has been evaluated by nitrogen sorption, which shows a high specific BET surface area of 700 m(2)/g and large uniform mesopores of ～4.3 nm. Both mesostructures and pore sizes can be tuned by changing the block copolymer templates or the ratio of resol to template. These free-standing mesoporous carbon films with cracking-free uniform morphology can be transferred or bent on different surfaces, especially with the aid of the soft polymer layer transfer technique, thus allowing for a variety of potential applications in electrochemistry and biomolecule separation. As a proof of concept, an electrochemical supercapacitor device directly made by the mesoporous carbon thin films shows a capacitance of 136 F/g at 0.5 A/g. Moreover, a nanofilter based on the carbon films has shown an excellent size-selective filtration of cytochrome c and bovine serum albumin.     

双模板法制备介孔／大孔复合孔结构硅胶独石

采用双模板法,向正硅酸甲酯的水解体系中同时引入聚乙二醇和三嵌段共聚物,成功制备出具有双连续大孔、同时孔壁中分布着有序介孔的复合孔结构硅胶独石材料. 产物的比表面积高达880 m2/g, 大孔孔径为0.2～5 μm, 介孔高度集中地分布在 5 nm. 结合物理吸附、扫描电镜、粉末X射线衍射和透射电镜等表征手段,发现合成条件如原料组成、反应温度和pH值等对反应体系中凝胶化转变和相分离发生的相对速度有重要影响,进而影响产物复合孔结构的生成. 此外,通过对合成条件的优化,一方面增强了无机骨架的强度,另一方面降低了湿凝胶干燥过程中的毛细管压力降,有效缓和了凝胶结构在干燥过程中的开裂和变形,使复合孔结构硅胶独石在厘米尺度内具有良好的整体性能.     

Features of Functionalization of MCM-41 Silica Mesoporous Molecular Sieves during Their Template Synthesis

We have shown that functionalization of MCM-41 mesoporous molecular sieves during their template synthesis using the effect of solubilization of organic hydrophobic co-condensing compounds makes it possible to obtain highly ordered mesoporous molecular sieves, with concentrations of vinyl or allyl groups covalently bonded to the surface of the silica matrix of about 3.5 mmol/g, which after sulfonation have acidic properties and exhibit catalytic activity in the process of ethyl tert-butyl ether synthesis.     

Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte

A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH < 2), thus facilitating the approach of hydrolyzed silica sol to the surface of the membrane, poly(sodium 4-styrenesulfonate) (Na+PSS-, denoted as PSS-) was used as an ionic linker. The use of PSS- led to a significant reduction in positive charge on the ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.     

A two-step route to synthesis of small-pored and thick-walled SBA-16-type mesoporous silica under mildly acidic conditions

Highly ordered SBA-16-type mesoporous silica materials were synthesized by using poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) triblock copolymer (EO(132)-PO(50)-EO(132), Pluronic F108) as template through a two-step pathway under mildly acidic conditions (pH 2.15-4.50). The highly ordered cage-like mesoporosity of the prepared SBA-16-type mesoporous silica materials having Im3m cubic mesostructure was proved by the well-defined X-ray diffraction patterns combined with transmission electron microscopy. Scanning electron microscopy shows a variation from the spherical agglomerations to the randomly shaped ones with an increase of pH value. The nitrogen adsorption-desorption analysis reveals that the prepared SBA-16-type mesoporous silica materials have a uniform small-sized pore diameter (3.37-4.24 nm) and very thick pore wall (8.84-10.2 nm). These features may make the SBA-16-type mesoporous silica materials synthesized in this study favor the incorporation of catalytically active heteroatoms in silica frameworks, and the functionalization of organic groups for applications in catalysis, sensor and separation. The two-step synthetic method under the mildly acidic conditions can also be extended to the production in the industrial scale as an environmentally friendly way.     

SBA-15负载CeO2纳米晶的溶胶-凝胶一步合成

以P123为模板剂, 正硅酸乙酯和硝酸铈为前驱体, 通过溶胶-凝胶路线在酸性条件下合成了SBA-15负载氧化铈(CeO2与SiO2质量比为28.7%)有序介孔材料. 采用热重/差热分析(TGA/DTA)、X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明, 合成的材料具有类似于SBA-15的结构, 孔径、孔容和比表面积分别为38.7 Å, 0.46 cm3/g和570 m2/g. X射线衍射(XRD)、透射电镜(TEM)、X射线能谱(EDS)和选区电子衍射花样联合表征证实了铈物种以高分散的CeO2纳米晶的形式分布在介孔基体中.     

Novel coassembly route to Cu-SiO2 MCM-41-like mesoporous materials

A series of mesostructured Cu-SiO2 composites have been synthesized with sodium metasilicate (Na2SiO3) and cuprammonia nitrate (Cu(NH3)4(NO3)2) respectively used as Si and Cu sources. The synthetic procedures were conducted at room temperature, and cetyltrimethylammonia bromide was used as a template. Under our experimental conditions, ordered mesoporous Cu-SiO2 composites could be obtained with a copper content up to 16.8 wt %. Average pore diameters (2.80-3.15 nm), wall thickness (1.30-2.20 nm), and specific surface area (1020-690 m2/g) are found to vary linearly with copper content (0-16.8 wt %). Results of thermal gravimetry-differential thermal analysis reveal the collapse temperature of the order structure starts at approximately 1250 K for mesoporous Cu-SiO2 with 16.8 wt % copper content. As indicated by the outcomes of inductively coupled plasma and X-ray photoelectron spectroscopy studies, copper is mainly incorporated inside the pore wall rather than embedded on the wall surface. Copper species strongly interact with silica, and calcination at high temperatures cannot cause phase separation between silica and copper oxide. Cu status in mesoporous Cu-SiO2 composites is similar to that in copper silicate in neighboring structures. Based on the results, a S+ I- I+ I- mechanism is proposed in which copper entities are surrounded by silicon species during synthesis of the mesostructured composite.     

Temperature Dependence in the Synthesis of SBA-16-Type Mesoporous Silica with Pluronic F68 Block Copolymer

By adjusting the local effective surfactant packing parameter through synthesis temperature, highly ordered SBA-16-type mesoporous silica materials have been synthesized by templating with a nonionic triblock copolymer Pluronic F68 in strongly acidic conditions at temperature 30～40°C with the addition of K₂SO₄. The prepared SBA-16-type mesoporous silica materials having Im3m cubic mesostructure were proved by the well-defined x-ray diffraction patterns combined with transmission electron microscopy. Scanning electron microscopy indicated that a transformation from faced-sphere to faced-polyhedron shape morphologies could be induced with increasing of the synthesis temperature. The nitrogen adsorption–desorption analysis revealed that the mean pore size (5.50～6.13 nm) of the prepared materials increased with increasing synthesis temperature. However, when the synthesis temperature exceeded 46°C, only disordered mesoporous silca was obtained. Our synthesis strategies by adjusting the local effective surfactant packing parameter through synthesis condition, even in a narrow range, would be used not only to optimize the synthesis conditions of reported mesoporous silca, but also to fabricate new mesoporous silica materials with well-ordered channel and anticipated morphologies.     

直接模板法合成三维立方介孔氧化硅HOM-5

0引言自1992年Mobil公司制备出M41S系列[1,2](包括MCM-41、MCM-48和MCM-50)介孔氧化硅以来,介孔材料以其有序度高、比表面积大、孔径可调等优异特性,引起了材料科学界的关注。不同类型的系列介孔材料,如SBA[3]、HMS[4]、MSU[5]等相继见诸报道。其中,空间群为Ia3d的MCM-48型三维立方介孔氧化硅具有完全相同,但互不相连的两套孔道[6],贯通性好,对称性高,对物料的传输优于二维孔道结构,在吸附、分离及催化等领域应用前景广泛。但这种结构对应的是溶致液晶相图的V1区域,对于多数表面活性剂来说,此相区较小,因此这种结构较难合成[7]。…     

由纳米晶前驱体组装有序介孔silicalite-1分子筛

采用两步法将不同尺寸的silicalite-1分子筛纳米晶种通过自组装合成了一系列有序介孔silicalite-1分子筛。首先将强碱性的silicalite-1前驱体分别加热不同时间得到纳米晶种,然后在类似合成SBA-15的强酸性条件下组装成有序的介孔材料。合成条件的剧烈变化阻止了分子筛晶种的继续长大,并在三嵌段共聚物模板的诱导下组装成有序介孔材料。这种“自下而上”的方法制备有序介孔分子筛同时包含微孔和介孔。氮气吸脱附结果表明所制备的介孔分子筛材料均表现了很大的比表面积(730 m2/g以上)。