有序介孔碳材料的制备研究及应用

有序介孔碳材料具有比表面积高、介观结构丰富、孔径均一可调等特点,在催化剂及催化剂载体、传感器和燃料电池等领域应用广泛。而模板法则是合成有序介孔碳材料的重要手段,其中硬模板法和软模板法各具特点。分别阐述了硬模板法和软模板法制备介孔碳材料的合成路线,并介绍了介孔碳材料在相关方面的应用现状。     

模板法合成中孔炭材料

在综合分析无机模板法和有机模板法的基础上,提出矿物模板法和复合模板法是制备中孔炭的有效方法.矿物模板法原料价格低廉、来源广泛.复合模板法综合了软模板和硬模板的优点,能够拓展中孔炭的结构、性能和应用领域.以矿物模板制备的炭材料具有良好的电学、医学性能等,有望获得良好性价比的中孔炭材料.     

常温催化消除CO获进展

正中科院兰州化学物理研究所唐志诚研究员课题组日前设计出一系列催化剂,并将它们成功应用于常温下CO的消除。课题组首先通过硬模板法制备了介孔和微孔二氧化铈,以及过渡金属掺杂的介孔二氧化铈基复合金属氧化物,并通过控制模板的合成条件实现对介孔金属氧化物的孔道定向设计。结果表明,制备的催化剂性能不仅与催化剂比表面积、     

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。     

有序介孔碳材料的制备及应用

有序介孔碳材料因具有较高的比表面积、均匀的孔径分布、有序的孔道结构排列等特性,成为催化、吸附、分离和电化学等领域的研究及应用热点。这里主要介绍了有序介孔碳的两种主要制备方法硬模板法和软模板法,以及其在催化、吸附及电化学等领域中的应用。     

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。     

软模板法合成介孔碳材料的研究与展望

介孔碳材料因其较高的比表面积,丰富的介观结构,高度有序的纳米孔道,已经引起了人们广泛的关注,因此在许多领域具有潜在的应用价值。软模板法合成介孔碳材料具有简单易行、成本低、结构可控等优点。目前采用最广泛的是溶剂挥发诱导自组装法和水热合成法,此文总结了这两种方法合成有序介孔碳材料的合成路线,阐述了其广泛的应用领域,并对有序介孔碳材料的合成与应用进行了展望。     

介孔炭材料及介孔炭/氧化硅复合材料对大分子有机污染物的吸附

介孔炭材料与活性炭相比具有较大的孔体积和孔径,高的比表面积以及规则的孔道结构,而介孔炭/氧化硅复合材料兼顾了活性炭与介孔材料的优点,因此在吸附大分子有机污染物方面有很好的应用前景。笔者综述了近年来介孔炭,负载/修饰后的介孔炭,介孔炭/氧化硅复合材料的制备和最新研究进展。在制备方面,根据其制备机理的不同可分为硬模板法和软模板法,制备出有序的介孔炭与介孔炭/氧化硅复合材料。在应用方面,重点介绍了介孔炭材料和介孔炭/氧化硅复合材料对大分子有机污染物的吸附性能。进而对介孔炭/氧化硅复合材料在吸附方面的应用进行了展望。     

有序纳米结构体系的模板合成法

利用具有特定结构的物质作为模板,来引导纳米有序结构的制备与组装,从而实现对纳米材料的组成、结构、形貌、尺寸、取向和排布等的控制,为研究纳米有序体系的性质提供了有利途径.模板可以分为软模板和硬模板两种,本文介绍了氧化铝、胶体晶体、胶束、生物大分子等几种常见模板的特点.利用模板法,可以制备金属、合金、氧化物、半导体和聚合物及其复合组份等多种纳米结构有序体系.本文结合我实验室最近的研究工作综述了利用模板法制备纳米有序结构体系的研究进展.     

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...     

聚乙二醇模板剂制备介孔材料的研究进展

聚乙二醇作为模板剂被广泛用于介孔材料的制备。介绍了使用单一聚乙二醇模板剂合成硅基、非硅基、复合类介孔材料的研究工作,探讨了聚乙二醇与表面活性剂、非表面活性剂类物质作复合模板剂制备介孔材料的方法。综述了聚乙二醇单一模板剂及复合模板剂制备介孔材料的机理。     

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.     

Ultrasonic-assisted synthesis and magnetic studies of iron oxide/MCM-41 nanocomposite

Iron oxide nanoparticles were stabilized within the pores of mesoporous silica MCM-41 amino-functionalized by a sonochemical method. Formation of iron oxide nanoparticles inside the mesoporous channels of amino-functionalized MCM-41 was realized by wet impregnation using iron nitrate, followed by calcinations at 550 °C in air. The effect of functionalization level on structural and magnetic properties of obtained nanocomposites was studied. The resulting materials were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy and selected area electron diffraction (HRTEM and SAED), vibrating sample and superconducting quantum interface magnetometers (VSM and SQUID) and nitrogen adsorption–desorption isotherms measurements. The HRTEM images reveal that the most of the iron oxide nanoparticles were dispersed inside the mesopores of silica matrix and the pore diameter of the amino-functionalized MCM-41 matrix dictates the particle size of iron oxide nanoparticles. The obtained material possesses mesoporous structure and interesting magnetic properties. Saturation magnetization value of magnetic iron oxide nanopatricles stabilized in MCM-41 amino-functionalized by in situ sonochemical synthesis was 1.84 emu g⁻¹. An important finding is that obtained magnetic nanocomposite materials exhibit enhanced magnetic properties than those of iron oxide/MCM-41 nanocomposite obtained by conventional method. The described method is providing a rather short preparation time and a narrow size distribution of iron oxide nanoparticles.     

Generation of mesoporosity in MOR zeolites synthesized under perturbation conditions

The hydrothermal synthesis of various mesoporous materials with mordenite (MOR) structures is performed under perturbation conditions involving varying-temperature crystallizations and the use of ternary organic templates, and at least three types of mesoporous materials are obtained from the same starting gel containing the ternary organic templates. The greater structural diversities of these materials are found to correlate remarkably with the second-staged crystallization temperature and time. Among these materials, the two mesoporous materials crystallized incompletely over low temperature periods are differently structural composites consisting of MOR crystallites within disordered mesoporous phases, whereas the mesoporous mordenite crystallized completely over relatively high temperature period possesses the intrinsic microporosity and hierarchical mesoporosity. TEM morphological investigations on the mesoporous mordenite crystals demonstrate the formation of intracrystalline mesopores. Furthermore, an entirely new approach to synthesize mesoporous MOR zeolites is proposed based on the pore-inducing role of MOR structure defects and the adequate perturbation towards synthesis conditions.     

表面活性剂模板法制备介孔材料

自从发现M41S系列介孔分子筛以来,人们对介孔材料的研究越来越活跃.在介孔材料的制备方面,用表面活性剂作模板来组装的方法有着重要的地位.对介孔材料的研究工作进行了简要介绍,讨论了介孔材料的形成机理、制备和影响介孔材料结构的因素.     

New families of mesoporous materials

Abstract

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 peptidehybridized 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.     

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.     

介孔二氧化硅纳米复合材料的研究进展

介绍了近年来介孔二氧化硅复合材料的研究趋势与发展方向。介孔二氧化硅材料作为研究时间最长、技术最成熟的介孔材料,对整个介观材料的理论和材料设计具有重要意义。阐述了介孔二氧化硅材料的主要合成方法及其原理,着重从材料复合方式以及相应材料的特点、相关应用等方面的研究进展进行了综述,探讨了现有的问题,并且对未来介孔材料的发展趋势进行了展望。     

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.     

中孔材料的研究进展Ⅰ:合成

近几年中孔材料的研究非常活跃，本文对中孔材料合成的最新进展进行了综述，从表面活性模板法和非表面活性剂模板法合成中孔材料两方面，对有关中孔材料骨架成分的调节，中孔材料形态及孔径的控制，以及提高中孔材料的水热稳定性等的最新研究成果进行了总结。