刚柔嵌段共聚物自组装制备有序孔材料研究进展

综述了刚柔嵌段共聚物自组装机理，以及近年来利用刚柔嵌段共聚物自组装制备有序孔材料的发展状况，指出刚柔嵌段共聚物制备有序孔材料的影响因素，认为刚柔嵌段共聚物自组装有着广阔的应用前景。     

聚合物模板法制备介孔材料

聚合物模板剂因其能够自组装成形态不同、尺寸可调的纳米单元,且在反应后易于除去等特点而在介孔材料的合成过程中起着重要的作用。本文中对近几年聚合物模板制备介孔材料的研究做了简要的回顾与总结,介绍了交联及嵌段共聚物、乳液及微乳液以及生物大分子作为模板制备介孔材料的研究进展,对现代物理测试技术如TEM、SEM、XRD和N2吸附-脱附曲线等在介孔材料的制备表征中的应用做了较详细的分析与探讨。     

纤维素纳米晶模板法制备有序介孔材料研究进展

纤维素纳米晶(cellulose nanocrysals,CNCs)是一种新型的模板材料,利用其自组装形成的手性结构可以实现CNCs模板法制备有序介孔材料。该法直接采用先驱体与具有自组装效应的CNCs复合并选择性去除模板或先驱体得到有序介孔,避免了预先制备介孔模板,缩短了工艺,并且对介孔结构可调性好。对应的介孔材料比表面积大、孔隙率高,介孔结构有序,为可控制备有序介孔材料提供了参考路径。介绍了CNCs的制备及其自组装,并且综述了近年来利用CNCs模板法制备有序介孔材料的研究进展,最后,对该领域未来研究方向进行了展望。     

有序介孔有机硅杂化材料的制备研究

分别采用两种不同的模板剂在不同的酸碱条件下成功地制备出有序介孔有机硅杂化材料,通过X射线衍射图谱、热失重分析和透射电子显微镜对制备的材料进行了表征,结果表明以嵌段共聚物和阳离子表面活性剂为模板剂均能成功制备出有序的介孔材料,而且所制得的材料具有优良的热稳定性,不同的有机官能团的引入大大地丰富了介孔材料的种类和用途.     

苯乙烯基嵌段共聚物在均孔膜中的应用

分离膜的孔径均一性决定着膜的分离精度,是目前高精度分离的研究热点。高分子嵌段共聚物具有自组装特点,通过微观相分离可以实现孔径均一的均孔膜的制备。其中,以苯乙烯基为代表的嵌段共聚物是目前使用最为普遍的均孔膜膜材料。基于此,本文从苯乙烯基嵌段共聚物膜材料的角度出发,归纳总结苯乙烯基嵌段共聚物均孔膜制备方法,并着重论述了国内外的苯乙烯基嵌段共聚物均孔膜的研究现状,详细介绍了非溶剂诱导相分离、选择性刻蚀、选择性去除和选择性溶胀的均孔膜制膜方法,并对其成膜过程进行阐述与分析。在此基础上,进一步探讨了利用苯乙烯基嵌段共聚物均孔膜的发展方向。     

新型两亲性嵌段共聚物导向合成有序大孔径介孔材料的研究进展

自从1992年首次报道介孔氧化硅分子筛M41S系列以来, 人们采用各种商业化表面活性剂为模板, 合成了多种骨架组成、丰富的有序介观结构、不同孔径尺寸的介孔材料, 并将其应用在能源、环境、催化等诸多领域。然而, 由于常规商业化模板剂的分子量大小有限, 合成的介孔材料具有较小的孔径(< 8.0 nm), 从而极大地限制了其面对大尺寸客体分子的相关应用。此外, 利用常规模板剂难以合成出具有晶化墙壁的介孔金属氧化物材料。近年来, 大分子量两亲性嵌段共聚物相继被报道用来合成新型介孔材料, 本文将综述基于这种嵌段共聚物为模板剂合成各种具有大孔径和晶化墙壁介孔材料的研究进展。     

以硅酸钠为前驱物用间隔自组装法制备等级介孔二氧化硅

以硅酸钠为前驱物,以三嵌段共聚物(P123)为模板剂,用间隔自组装法(即PCSA法)制备了具有等级孔结构的介孔二氧化硅。结果表明:间隔条件等级孔结构的形成起到了关键作用,在加入量合适和间隔时间条件下间隔法允许在不使用添加剂、复合模板剂及特殊的制备条件下使用较廉价的硅酸钠制备有序的等级介孔二氧化硅。等级介孔二氧化硅的第一级介孔孔径约9 nm,第二级大孔径分布较宽,介于20-200 nm。而在特定的间隔条件下(SS6-4h-4.5与SS3-4h-7.5),可制备出第一级有序的等级介孔二氧化硅。     

基于低聚酰亚胺含氮介孔碳材料的制备

以低聚酰亚胺为氮源前驱体、交联酚醛树脂为碳源、嵌段共聚物为软模板剂,通过相分离自组装、交联和高温锻烧处理制备了新型高规整含氮介孔碳材料,并用FT-IR、SEM、TEM、热重分析和小角X光散射等测试方法表征介孔碳材料的组成与结构.结果表明,处理温度达350℃时嵌段共聚物模板可被成功移除,进而形成多孔结构;温度达600℃时体系完全碳化,可得到高规整的多孔含氮碳材料.通过调节体系中氮源、碳源及模板剂的相对比例可实现形貌由立方结构向柱状和层状结构的过渡,进而实现对含氮介孔材料形貌的有效调控.     

嵌段共聚物自组装模板--构造纳米结构的一种新方法

纳米结构的构造在整个纳米科技中有着特殊重要的意义．如何低成本、大规模地实现纳米结构材料的控制合成与组装一直是纳米加工中的热点问题．高分子嵌段共聚物分子结构独特，包含着热力学不相容的不同高分子嵌段，并由化学键相连．通过控制外界条件，嵌段共聚物可以自组装成高度规则的超分子结构，特征尺寸为10nln～100nm．以嵌段共聚物膜自组装相分离图案为模板，或把这种图案复制到其它材料上，通过刻蚀等技术可以制备纳米结构模板，再经纳米铸造得到相应结构的纳米材料和纳米器件，文中主要介绍嵌段共聚物自组装模板的原理、模板图案的调控方法和模板应用，并详细阐述了各自的发展状况。     

定向嵌段共聚物薄膜制备纳米孔阵列模板

探索了纳米孔阵列模板制备的新技术--一种基于电场作用下嵌段共聚物薄膜的自组装.采用阴离子聚合技术,以苯乙烯(St)和甲基丙烯酸甲酯(MMA)为单体制备了一定嵌段比例的二嵌段共聚物P(St-b-MMA).GPC分析表明其分子量为23000～49000、分子量分散度在1.06～1.2,1H NMR、FTIR等分析表明共聚物具有嵌段结构成分.共聚物离心涂膜并在电场作用下的自组装,选择性地刻蚀后获得了可控的纳米尺寸孔洞的阵列,SEM、AFM、UV-vis等分析表明阵列模板中孔洞大小为25～800nm,孔密度可达4×108/cm2.     

Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation

Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.     

缓冲溶液中制备掺杂高度隔离铁物种的介孔氧化硅(英文)

使用P123作为模板剂,采用不同的硅源(正硅酸甲酯,正硅酸乙酯,硅酸钠)在弱酸性的条件下(pH=4.4,乙酸-乙酸钠缓冲溶液)合成掺杂铁的介孔氧化硅材料.正硅酸甲酯和硅酸钠形成有序的二维六方相的介孔结构,而正硅酸乙酯形成了囊泡结构.紫外可见漫反射光谱和紫外共振拉曼光谱表明,在环境友好的条件下,采用硝酸铁和硅酸钠可以合成出高度隔离的铁物种.缓冲溶液提供了一条便捷的途径,通过简单改变硅源来控制介孔结构.掺杂铁的介孔氧化硅材料在苯酚的羟化反应中表现出优异的催化性能,主要由于铁物种高度分散在氧化硅载体上,介孔结构使铁活性位更易于接近反应物分子.     

One-pot synthesis of ordered mesoporous carbon–silica nanocomposites templated by mixed amphiphilic block copolymers

Mixed amphiphilic block copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO–PPO–PEO) and polydimethylsiloxane-poly(ethylene oxide) (PDMS–PEO) have been successfully used as co-templates to prepare ordered mesoporous polymer–silica and carbon–silica nanocomposites by using phenolic resol polymer as a carbon precursor via the strategy of evaporation-induced self-assembly (EISA). The ordered mesoporous materials of 2-D hexagonal (p6m) mesostructures have been achieved, as confirmed by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and nitrogen-sorption measurements. Experiments show that using PDMS–PEO as co-template can enlarge the pore sizes and reduce the framework shrinkage of the materials without evident effect on the specific surface areas. Ordered mesoporous carbons can then be obtained with large pore sizes of 6.7 nm, pore volumes of 0.52 cm³/g, and high surface areas of 578 m²/g. The mixed micelles formed between the hydrophobic PDMS groups and the PPO chains of the F127 molecules should be responsible for the variation of the pore sizes of the resulting mesoporous materials. Through the study of characteristics of mesoporous carbon and mesoporous silica derived from mother carbon–silica nanocomposites, we think mesoporous carbon–silica nanocomposites with the silica-coating mesostructure can be formed after the pyrolysis of the PDMS–PEO diblock copolymer during surfactant removal process. Such method can be thought as the combination of surfactant removal and silica incorporation into one-step. This simple one-pot route provides a pathway for large-scale convenient synthesis of ordered mesostructured nanocomposite materials.     

Synthesis of highly ordered and hydrothermally stable mesoporous materials using sodium silicate as a precursor

Highly ordered mesoporous silica and aluminosilicate materials with extremely high hydrothermal stability have been synthesized successfully at a high hydrothermal treatment temperature of 200 °C by using inexpensive sodium silicate and sodium aluminate as the silica source and alumina source, respectively. The resultant mesoporous materials possess a hexagonal mesostructure and extraordinary stability towards the steam treatment at 800 °C for 2 h. In addition, the direct incorporation of Al into the mesoporous framework can further enhance the hydrothermal stability of ordered mesoporous materials. Our contribution provides a commercially important approach to synthesize ordered mesoporous materials with highly hydrothermal stability, which may find potential applications for the catalytic cracking in the petroleum industry.     

有序介孔二氧化钛粉体研究进展

主要综述了高度有序六方相和立方相孔道结构介孔二氧化钛以及具有低有序蠕虫状孔道结构介孔二氧化钛的制备方法及其结构特征。总结了后处理法、模板剂脱除法在制备稳定、具有有序介孔和锐钛矿相孔壁的介孔二氧化钛粉体中的应用,指出采用直接合成法制备孔壁结晶的介孔二氧化钛原粉,之后用萃取法脱除模板剂并用钛酸异丙酯蒸气增强骨架,将是得到高稳定性有序介孔二氧化钛材料的良好途径。     

Multiscale Phase Separations for Hierarchically Ordered Macro/Mesostructured Metal Oxides

Porous architectures play an important role in various applications of inorganic materials. Several attempts to develop mesoporous materials with controlled macrostructures have been reported, but they usually require complicated multiple‐step procedures, which limits their versatility and suitability for mass production. Here, a simple approach for controlling the macrostructures of mesoporous materials, without templates for the macropores, is reported. The controlled solvent evaporation induces both macrophase separation via spinodal decomposition and mesophase separation via block copolymer self‐assembly, leading to the formation of hierarchically porous metal oxides with periodic macro/mesostructures. In addition, using this method, macrostructures of mesoporous metal oxides are controlled into spheres and mesoporous powders containing isolated macropores. Nanocomputed tomography, focused ion beam milling, and electron microscopy confirm well‐defined macrostructures containing mesopores. Among the various porous structures, hierarchically macro/mesoporous metal oxide is employed as an anode material in lithium‐ion batteries. The present approach could provide a broad and easily accessible platform for the manufacturing of mesoporous inorganic materials with different macrostructures.     

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.     

Synthesis and photochromism of tungstophosphate-functionalized ordered mesoporous hybrid silica

New tungstophosphate-functionalized ordered mesoporous silica was synthesized based on monovacant PW11 and block copolymer template. Upon characterizations of the as-obtained PW11/MHS samples by FT-IR, XRD, ICP-AES and N2 adsorption-desorption measurements, it was revealed that Keggin units were retained perfectly in hexagonally symmetrical mesopore channels and bound covalently onto the pore walls of mesoporous silica. The material exhibits stable and reversible photochromic property upon UV irradiation even though no a special organic component was supplied as electron donor. This may provide a new approach to construct photochromic materials of potential applications in high-density optical memories and other optical devices.     

Correlation between the capacitor performance and pore structure of ordered mesoporous carbons

Mesoporous carbons were synthesized by organic–organic self-assembly of triblock copolymer F127 and phenolic resin oligomers composed of resorcinol–formaldehyde or resorcinol–furfural. The mesostructure control was performed by using different polymerization catalysts, ammonia and acetic acid. The effects of the aldehyde and polymerization catalyst on pore architecture of mesoporous carbons were investigated. Disordered mesostructure with poorly disconnected mesopores was formed using furfural. In contrast, when formaldehyde was used, ordered structure with mesochannels was formed. In addition, changes in mesochannel length and the degree of long-range order are found to depend on polymerization catalyst. The porous carbons with different structure were used as a model material to investigate the ion storage/transfer behavior in electrical double-layer capacitor. Electrochemical cyclic voltammetry measurements were conducted in 1 M sulfuric acid electrolyte solution. The ordered mesoporous carbons show superior capacitances and rate performance over the disordered carbons. Electrochemical impedance spectroscopy was used to assess the transport properties. The impedance data clearly demonstrated that the degree of long-range order and channel length can influence the ion transport, resulting in superior capacitive performances.