New families of mesoporous materials

Mesoporous materials have been paid much attention in both scientific researches and practical applications. In this review, we focus on recent developments on preparation and functionalization of new families of mesoporous materials, especially non-siliceous mesoporous materials invented in our research group. Replica synthesis is known as the method to synthesize mesoporous materials composed of various elements using originally prepared mesoporous replica. This strategy has been applied for the syntheses of novel mesoporous materials such as carbon nanocage and mesoporous carbon nitride. Carbon nanocage has a cage-type structure with huge surface area and pore volume, which exhibits superior capabilities for biomolecular adsorption. Mesoporous carbon nitride was synthesized, for first time, by using mixed material source of carbon and nitrogen simultaneously. As a totally new strategy for synthesis of mesoporous materials, the elemental substitution method has been recently proposed by us. Direct substitution of component elements in original mesoporous materials, with maintaining structural regularity, provided novel mesoporous materials. According to this synthetic strategy, mesoporous boron nitride and mesoporous boron carbon nitride have been successfully prepared, for first time. In addition to these material inventions, hybridization of high functional materials, such as biomaterials, to mesoporous structure has been also developed. Especially, immobilization of proteins in mesopores was systematically researched, and preparation of peptide-hybridized mesoporous silica was demonstrated. These new families of mesoporous materials introduced in this review would have high potentials in future practical applications in wide ranges from electronics and photonics to environmental and medical uses.     

Recent progress in mesoporous titania materials: adjusting morphology for innovative applications

Abstract

This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.     

一步模板炭化法制备新型沥青基中孔炭材料

以乙酸镁和柠檬酸镁为模板(MgO)镁源,沥青为碳前驱体,在氮气氛中950℃一步炭化制得高表面积中孔炭材料.采用1 mol/L的HCl去模,并将炭材料洗涤至中性.采用低温N2吸附测得炭材料的比表面积和孔径分布,透射电镜观察炭材料的内部结构特征.结果表明:尽管未经活化,所得炭材料中的孔大多为中孔,BET比表而积达到1295 m2/g,当以柠檬酸镁为MgO前驱体时,所得炭材料的收率可高达50%.     

A dual template method for synthesizing hollow silica spheres with mesoporous shells

PS/silica core/shell composites were synthesized by the modified Stöber method using polystyrene spheres and cetyltrimethylammonium bromide as dual templates under room temperature. The silicate species and the templates were self-assembled to form mesoporous silica shell on the surface of the PS spheres. Hollow silica spheres with mesoporous shell were obtained by removing the polymer core and the templates through calcination. The hollow silica spheres showed high specific surface area of 1099.5 m²/g and narrow pore size distribution centered at 2.31 nm.     

结构有序、双重孔隙中孔炭材料的合成与表征

采用纳米涂层技术,以介孔分子筛SBA 15为模板,在其纳米孔道内引入糠醇/草酸溶液,经原位聚合,炭化后制得炭/SBA 15复合物。采用化学法脱除模板后制得具有规则结构的中孔炭。高分辨TEM表征结果显示该中孔炭是由纳米炭管相互联接、堆积而成,且具有六方对称结构。氮吸附结果显示其比表面积高达2000m2/g,孔径呈双峰分布。孔径相对较大的孔隙来源于SBA 15孔道经纳米涂层后所保留的孔隙;孔径相对较小的孔隙来源于SiO2移除后遗留的纳米孔空间。该方法可应用于以其他多孔氧化硅为模板制备新型纳米复合物的研究过程。     

非水体系快速挥发法直接合成有序介孔炭

采用非水溶剂快速挥发法,以表面活性剂和酚醛树脂为结构导向剂和碳前驱体制备介孔炭.通过透射电镜、氮吸附-脱附和扫描电镜对产品的结构进行了表征.结果表明:所制介孔炭具有高度有序的二维六方结构.表面活性剂与酚醛树脂的配比对介孔炭的有序性有较大的影响,当其质量比高于1:0.25时,可保持良好的有序度.随着比值的减小,有序度逐渐降低.与蔗糖液相浸渍法相比,非水体系快速挥发法所制介孔炭具有较少的外微及大孔.     

介孔炭材料应用于电化学催化的研究进展

由于介孔炭材料具有高比表面、均一可调的孔径尺寸和形貌、良好的导电性和化学稳定性等优点,已被广泛应用到催化、吸附、分离和电化学储能等领域.近年来,多组分的掺杂与复合使介孔炭材料拥有可调变的功能性,已成为材料领域研究的一个热点.本文首先介绍介孔炭材料的合成,包括软模板法、硬模板法和无模板法等.接着论述介孔炭及其复合材料在电...     

Synthesis and characterization of surface-modified and organic-functionalized MCM-41 type ordered mesoporous materials

A new and efficient method for the preparation of MCM-41 type ordered mesoporous phases using phosphate as promoter under reflux conditions is reported. The various mesoporous materials studied were: silica (Si-MCM-41), alumino-silicate (Al-MCM-41), and titanium-silicate (Ti-MCM-41). Our concept of promoter-assisted synthesis of zeolites and related microporous materials was found to be applicable in the synthesis of ordered mesoporous materials as well. The addition of small catalytic quantity of phosphate ions (PO ₄ ³⁻ ), used as promoters, significantly reduced the synthesis time (by a factor of 3–4) of all these mesoporous materials. The synthesis of new MCM-41 type organic-inorganic composite materials with unique properties is also reported.     

Critical effect of aging condition on mesostructural ordering in mesoporous titania thin film

Here we demonstrate facile synthesis method for formation of highly ordered mesoporous cubic Im-3 m titania thin film. The mesostructural ordering is strongly dependent on the aging condition after the spin-coating. The aging condition under low temperature and low humidity is found as an optimum condition for achieving highly ordered mesostructure in titania thin films. The effects of other important synthetic parameters, such as pH of the precursor solutions and aging periods, on the mesostructural ordering are carefully examined. After the calcination, continuous mesoporous films with partially crystallized frameworks are formed without any cracks. The mesostructure of the calcined films is formed by thermal shrinkage of the original Im-3 m mesostructure. The mesostructural change in the films calcined at various temperatures are studied by using the grazing-incidence small-angle X-ray scattering (GI-SAXS). The GI-SAXS patterns show the strong shrinkage along the perpendicular direction to the substrate by increasing the calcination temperature.     

模板法制备沥青烯基有序结构中孔炭

以煤炭直接液化工艺过程的副产物--沥青烯为碳源,中孔硅分子筛SBA-15为模板,采用模板炭化法制备了具有规则结构的中孔炭.制备过程包括利用溶剂夹带法将沥青烯填充到模板孔道内,炭化模板孔道内的沥青烯以及脱除模板等步骤.利用扫描电镜、透射电镜、粉末X射线衍射仪对产品的微观形貌和结构进行了分析;测定了材料的抗氧化性能、导电性能以及对N2的吸附特性.结果表明:产品具有对模板结构反转复制的规则结构,其比表面积为562m2/g,孔容为0.566cm3/g,孔尺寸呈单分布,平均孔径为3.57nm;此外,材料具有良好的抗氧化性能,空气环境下300℃处理后样品仍保持规则的孔结构形态;其平均电阻率为0.16Ω*cm左右,属半导体材料导电性能范畴.     

On the facile polyvinyl alcohol assisted sol-gel synthesis of tetragonal zirconia nanopowder with mesoporous structure

A facile template assisted sol-gel method has been used to prepare nanoparticles of tetragonal zirconia (t-ZrO₂) with spherical morphology and porous structure along with mono dispersibility. The medium assisting growth of nanoparticles mainly consisted of ZrOCl₂·8H₂O and NH₄OH as reactants in a 1:2 mixture of Isopropyl alcohol (IPA)-polyvinyl alcohol (PVA) as the dispersing agent. The effect of medium, IPA-PVA mixture on crystallite size and agglomeration was studied and discussed on the basis of XRD and also based on possible surface reactions. More over reacting medium and calcination temperature has vital role in determining the crystallinity and morphology of ZrO₂. Trials based on mode of addition of the reacting medium followed by calcination provides mesoporous, spheroid, monoclinic zirconia (m-ZrO₂) with an average particle size of 15?nm. The sample prepared under optimized conditions (2?wt% PVA-IPA) showed pure tetragonal crystallite phase with an average particle size of 5?nm, surface area of 56?m²?g^?1, and a mesoporous structure after calcination at 600?°C for 5?h. The tetragonal (t-ZrO₂) phase formed were stable and showed spherical morphology up to 600?°C after which the nanostructure was disturbed drastically; the agglomeration leads to structure collapse forming hard conglomerates and finally leads to monoclinic crystalline phase.     

模板法中孔炭及其双电层电容性能(英文)

以乙酸镁和柠檬酸镁热解得到的MgO为模板,热塑性沥青为碳前驱体,采用程序升温一步炭化法(950℃,N2)制备了高比表面积中孔炭材料。尽管未进行活化,两种模板前驱体与沥青混合所制中孔炭材料均可获得非常高的比表面积。以这两种中孔炭作为双电层电容器的电极材料,在质量分数为30%的KOH电解液中测试其电化学性能。结果表明:这两种中孔炭电极均可得到较高的比电容量和理想的功率特性,尤其是柠檬酸镁作前驱体时,MgO与沥青质量比为4时得到的炭材料(MCP8/2)在20mA.g-1的电流密度下得到284F.g-1的比电容量,且在1000mA.g-1时仍能得到236F.g-1的比电容。交流阻抗测试表明:组装的双电层电容器的内部阻抗均小于3.5Ω。     

Synthesis and characterization of ordered mesoporous silica by using polystyrene microemulsion as templates

A simple room temperature synthesis of pure mesoporous silica by using a homemade and functional template: polystyrene microemulsion is reported. The process consists of HCl-catalysed sol-gel reactions of tetraethyl orthosilicate (TEOS) in polystyrene microemulsion, followed by removal of the template via solvent extraction or calcining. X-ray diffraction, Transmission Electron Microscope and N₂ adsorption-desorption isotherms are then used to characterize the mesostructure. The results indicate that the synthesized mesoporous silica has a large BET surface area with more than 900 m²/g, large pore volume with more than 0.8 cm³/g and ordered mesopore-structure. This provides a possible way to control the meso-structure and pore size of mesoporous materials via potential functional templates.     

The preparation of Ag/mesoporous silica by direct silver reduction and Ag/functionalized mesoporous silica by in situ formation of adsorbed silver

Mesoporous silica (MS) with large pores and thiol functionalized mesoporous silica (TFMS) were synthesized. ²⁹Si MAS NMR confirmed the functionalization of MPTMS on the surface of mesoporous silica. Silver nanoparticles were prepared by two methods: (1) direct reduction of Ag⁺ ions with NaBH₄ in aqueous AgNO₃ solution containing MS, (2) in situ reduction of Ag⁺ ions adsorbed on TFMS with NaBH₄. The characteristics of products from both methods were compared using SAXRD, TEM, and N₂ adsorption-desorption. Ag nanoclusters were mostly confined and dispersed in the channels of the TFMS and their sizes were under 6 nm. However, Ag nanoparticles on the MS formed outside the mesoporous channels rather than within them.     

Characterization and acidic properties of Al-SBA-3 mesoporous material

SBA-3 mesostructured silica containing framework aluminum is reported here. This material was successfully synthesized using sodium aluminate via post synthesis method. The structural properties of this novel material were studied by X-ray diffraction and FTIR. The Al insertion was determined by ²⁷Al-NMR and the acidity was monitored by infrared spectroscopy of Pyridine adsorption/desorption. The ²⁷Al NMR results indicate that Al has been effectively incorporated into the framework of SBA-3 material by post-synthesis method. The bridging hydroxyl (Si₃O-Al-OH) acid sites are observed after the adsorption of basic probe molecules, such as pyridine; this fact strongly supports the presence of Bronsted acid sites. The alumination of Si-SBA-3 produces stronger Brønsted acidity than the conventional mesoporous aluminosilicates.