有机-无机杂化介孔二氧化硅的合成及应用

有机-无机杂化介孔材料因其具有显著的活性中心、较高的机械和水热稳定性等特点,成为国内外学者广泛关注的热点研究材料。综述了有机-无机杂化介孔二氧化硅材料的主要合成方法,包括后合成法、共缩聚法和有序介孔有机硅法,并对3种方法存在的优缺点进行了比较。同时详细介绍了有机-无机杂化介孔二氧化硅材料在催化、环境保护、生物医药和光学领域的应用。并展望了有机-无机杂化介孔二氧化硅材料的发展及应用前景。     

有机-无机杂化介孔二氧化硅的合成及应用

有机-无机杂化介孔材料因其具有显著的活性中心、较高的机械和水热稳定性等特点,成为国内外学者广泛关注的热点研究材料。综述了有机-无机杂化介孔二氧化硅材料的主要合成方法,包括后合成法、共缩聚法和有序介孔有机硅法,并对3种方法存在的优缺点进行了比较。同时详细介绍了有机-无机杂化介孔二氧化硅材料在催化、环境保护、生物医药和光学领域的应用。并展望了有机-无机杂化介孔二氧化硅材料的发展及应用前景。     

β-环糊精修饰的乙烷桥键有序介孔有机硅材料的合成及应用

该文用“嫁接”的方法将β-环糊精（β-CD）修饰在乙烷桥键有序介孔有机硅材料（PMO）上,并以同样的方法合成了β-CD修饰的介孔材料SBA-15作为对比材料。通过傅里叶红外光谱（FTIR）、高分辨透射电镜（HRTEM）、X射线粉末衍射（XRD）、氮气吸附以及热分析（TGA）实验对修饰前后的PMO材料进行表征。考察了修饰前后PMO材料对于水中污染物苯胺和对苯二酚的吸附性能,由结果可知,β-CD修饰的乙烷桥键有序介孔有机硅材料（PMO-CD）对于苯胺的吸附量为1.54mg/g,相对于PMO材料而言,其吸附能力被极大的抑制,而其对于对苯二酚的吸附量为12.94mg/g,吸附性能得到了很大的提高。因此,PMO-CD在处理水中污染物领域具有潜在的应用价值。     

稀土有机配合物/聚倍半硅氧烷的制备及发光性能研究

桥联聚倍半硅氧烷是有机-无机杂化材料中具有特殊性能的一类新型杂化材料。稀土有机配合物单色性好,色纯度高。将稀土有机配合物与桥联聚倍半硅氧烷有机的结合起来制备杂化材料,在理论研究和实际应用中都具有重要意义。本文合成了含有5-氨基间苯二甲酸基团桥联单体,并以单体作为前驱体,在稀土离子存在的情况下,通过溶胶-凝胶过程制得含有稀土配合物的桥联聚倍半硅氧烷。利用红外光谱以及荧光光谱对材料进行表征。研究表明,置于桥联聚倍半硅氧烷的5-氨基间苯二甲酸能够有效地敏化稀土离子发光。     

β-环糊精修饰的乙烷桥键有序介孔有机硅材料的合成改性及应用

该文用"嫁接"的方法将β-环糊精(β-CD)修饰在乙烷桥键有序介孔有机硅材料(PMO)上,并以同样的方法合成了β-CD修饰的介孔材料SBA-15作为对比材料。通过傅里叶变换红外光谱(FTIR)、高分辨透射电镜(HRTEM)、X射线粉末衍射(XRD)、氮气吸附以及热分析(TGA)对修饰前后的PMO材料进行表征。考察了修饰前后PMO材料对于水中污染物苯胺和对苯二酚的吸附性能,由结果可知,β-CD修饰的乙烷桥键有序介孔有机硅材料(PMO-CD)对于苯胺的吸附量为1.54 mg/g,相对于PMO材料而言,β-CD的修饰使其吸附能力被极大地抑制,而其对于对苯二酚的吸附量为12.94 mg/g,吸附性能得到了很大提高。因此,PMO-CD在处理水中污染物领域具有潜在的应用价值。     

合成二维六方苯环桥联型杂化介孔材料的新方法

以苯基桥联硅氧烷[1,4-bis(trimethoxysily1)benzene,BTSB]和三嵌段共聚物聚氧乙烯-聚氧丙烯-聚氧乙烯(EO20PO70EO20,P123)分别作为硅源和模板剂,在无酸体系中利用ZrOCl2-K2SO4的协同作用方便制得二维六方苯环桥联型杂化介孔材料(periodic mesoporou...     

介孔炭的合成及应用研究进展

综述了介孔炭的合成方法及介孔炭的应用,重点介绍了模板合成法,包括无机模板法,中孔分子筛模板法和有机模板法,指出有机模板法工艺简单,发展前景可观。介孔炭具有很广泛的用途,其中,作为催化剂载体的研究应该得到充分重视,同时介孔碳在储氢、储能材料方面的应用可能成为未来的研究热点。     

介孔分子筛改性及在吸附脱硫中的应用

介孔分子筛由于具有较大的比表面积、孔容、孔径等优点使得其在吸附分离等领域得到了广泛的应用。本文综述了介孔分子筛改性的不同方法,包括嵌入法、负载法,以及有机-无机杂化介孔材料的制备等。对介孔分子筛在吸附脱硫方面的最新研究进展进行了总结,包括对燃料油、天然气、煤气中硫化物的吸附脱除,以及H2S、SO2等大气污染物的吸附脱除。同时对介孔分子筛的改性及发展前景进行了展望,合成新型有机-无机杂化介孔材料并将其应用于吸附等领域是未来发展的主要趋势。     

磺酸基功能化的双金属掺杂介孔材料HSO_3-Zr-La-SBA-15催化酯水解反应的应用

以3-巯丙基-三甲氧基硅烷为有机功能试剂,采用后接枝法,合成了磺酸基功能化的介孔材料HSO3-ZLS。制备的磺酸基功能化介孔材料对羧酸酯水解的催化性能研究表明,功能化的新型介孔材料催化活性高,是环境友好型催化剂。     

不同方法脱除介孔氧化硅有机模板剂

介孔材料发展至今,模板剂的去除问题一直都没有得到解决,为了更好的解决去除介孔氧化硅有机模板剂的问题,文章拟采用煅烧、萃取和煅烧-萃取结合的方法脱除介孔氧化硅的有机模板剂.通过透射电镜(TEM)、氮气吸附/脱附和傅里叶红外和热重等表征手段对材料的结构特性进行分析,结果表明450 ℃煅烧得到的材料孔径(4.8 nm)、孔容(0.558 cm3· g-1)及比表面积(604.64 m2· g-1)是最大的.文章对这几种方法进行了系统研究.得到的结论对如何快速选择去除模板剂的方法具有指导性意义.     

Synthesis chemistry and application development of periodic mesoporous organosilicas

This paper provides a comprehensive and critical overview of recent advances in synthesis chemistry and application development of periodic mesoporous organosilicas (PMOs). A number of organic bridge-bonded functional and multifunctional PMOs with inorganic–organic hybridized framework have been synthesized from varieties of precursors. The syntheses of a series of PMOs have been accomplished typically by resorting to the co-condensation of the mixed precursors of tetraalkoxysilane and bridged organosiloxane, bridged organosiloxane with terminal organosiloxane, or the co-condensation of multiple bridged organosiloxane. The choice of precursors depends on the desired location of organic groups which can be either on the surface or within the pore wall in resulting PMOs. Besides precursors, synthesis conditions evidently play an important role in the formation, morphologies and pore structure of PMOs. Recent advances show that the morphologies and mesopores of PMOs can be adjusted by changing the synthetic parameters such as template, additives, pH value, and temperature. The PMOs with tunable composition, morphology and even-distributed hydrophobic organic groups in the framework endow such periodic mesoporous hybrids with great potentials in the fields of catalysis, environmental remediation, biology, pharmacy, analytical chemistry and microelectronics. The synthesis chemistry of PMOs and application development would particularly and continuously appeal to the researchers in chemistry and materials science in future.     

Past, present, and future of periodic mesoporous organosilicas-the PMOs

Periodic mesoporous organosilicas (PMOs) represent an exciting new class of organic-inorganic nanocomposites targeted for a broad range of applications such as catalysis and sensing, separations, and microelectronics. Their hallmark is the presence of organic bridging groups incorporated into the channel walls of an ordered nanoporous structure, which represents a useful tool to finely tune the chemical and physical properties of the materials. We discuss the history of the discovery and development of the PMOs emphasizing the most important recent advancements regarding compositions and structures, morphologies, and properties. Furthermore, we present an outlook about the promising future perspectives of PMOs that result from the latest developments in this field.     

介孔碳的研究进展及应用

介孔碳是一类新型的具有巨大比表面积和孔体积的介孔材料,可以通过不同的方法合成并对其孔结构和形貌进行调节。本文主要综述了介孔碳及介孔碳基复合材料的合成方法,对比阐述了不同方法制备的介孔碳材料所具备的孔道结构和形貌。介绍了将不同非金属和金属元素及其氧化物掺杂在介孔碳中合成复合材料,发现制备的复合材料具有更优的性能且掺杂元素不同复合材料的形貌和孔道结构不同。此外,简要说明了介孔碳及碳基复合材料在环境、催化、储能、电化学和生物医学等方面的应用,指出其在各个领域的应用仍存在不足。调整介孔碳的孔结构和表面性能、采用更简便易控制的合成方法将成为制备介孔碳及碳基材料的主要研究方向。     

PMOs／PMMA纳米复合材料的制备及性能研究

采用低温水热合成法合成周期性介孔有机硅（PM0s）材料,并制备了具有网络结构的PMOs／PMMA纳米复合材料。通过Fr—IR、XRD、TEM和SEM等方法对其结构和性能进行了表征。结果表明：通过改变1,2-双-三氧基硅基乙烷（BTESE）的物质的量比例,可获得宏观形貌从立方（Fm3m）结构变化到纳米空心小球的一系列PMOs材料。在PMOs／PMMA纳米复合材料中,PMOs仍保持其原有的介观结构。在PMOs含量较低时对PMMA拉伸强度和模量、弯曲强度和模量增强作用较为明显,但增韧效果较差。     

Synthesis of SBA-15 type mesoporous organosilicas with diethylenebenzene in the framework and post-synthetic framework modification

The SBA-15 type periodic mesoporous organosilicas (PMOs) containing different fraction of 1,4-diethylenebenzene groups in the framework were synthesized by co-condensation of 1,4-bis(trimethoxysilylethyl)benzene with tetramethoxysilane under acidic conditions using triblock copolymer Pluronic P123 as structural directing agent. The results of X-ray diffraction pattern (XRD), nitrogen sorption isotherm, and transmission electron microscopy (TEM) show that all materials have well-ordered mesoporous structure with uniform pore size distributions. The acidic sites were incorporated in the mesoporous framework by post-synthetic framework modification of 1,4-diethylenebenzene by sulfonation. The framework composition of the mesoporous organosilicas before and after modification was fully characterized by UV Raman spectroscopy, and ¹³C CP-MAS and ²⁹Si MAS NMR. From elemental analysis, it can be estimated that about 40% of the organic group within the mesoporous framework is available for further chemical reaction. The PMOs with aryl sulfonaic acid groups in the framework are efficient solid acids for the esterification of ethanol with aliphatic acid. With the alkyl chain of the aliphatic acid increasing, the activity of the material is enhanced by more amounts of 1,4-diethylenebenzene incorporated in the mesoporous framework. The post-synthetic modification is a facile approach for the generation of new functional groups in the mesoporous framewrok of PMOs.     

Catalytically active gold nanoparticles confined in periodic mesoporous organosilica (PMOs) by a modified external passivation route

A modified external passivation route was performed to control the distribution of gold nanoparticles in periodic mesoporous organosilica (PMOs). The surfactants were first removed completely to ensure enough space in the mesopores. The external surface was then functionalized with n-octadecyltrimethoxysilane (C₁₈TMS), and finally the internal surface was modified with aminopropyltrimethoxysilane (APTMS) to enhance the adsorption of (HAuCl₄)^? complex, followed by the reduction under hydrogen atmosphere. The external passivation aims to prevent the formation of large aggregated gold particles on the exterior surface. The aminopropyl groups at the internal surface ensure the incorporation of gold nanoparticles with a size about 5 nm inside the pore channels of PMOs. A combination of high-resolution TEM/STEM and SEM shows that the selective surface functionalization can effectively avoid the growth of large gold particles at the external surface and strictly confine the gold nanoparticles within the pore channels of PMOs. The confined gold nanoparticles in PMOs exhibit good catalytic properties in the reduction of methylene blue (MB) dye with sodium boron hydride as reducing agent.     

功能化有序介孔有机硅催化剂的合成与应用

介绍了近年来研究开发的新型有序介孔有机硅PMOs催化材料,着重介绍了此类材料作为固体酸性催化剂、固体碱性催化剂、手性催化剂和金属杂化催化剂的制备和功能化方法,评述了此类材料作为催化剂的应用试验结果,分析了功能化PMOs催化剂与其催化性能之间的构效关系,并展望了该类材料在催化科学和工业中的开发和应用前景。     

An overview of ordered mesoporous material SBA-15: synthesis,functionalization and application in oxidation reactions

Ordered mesoporous materials are attracting wide concern because of their applications in the field of catalysis, adsorption, separations, drug delivery systems and gas sensors owing of their extremely high surface area combined with well-defined pore structures with narrow pore size distributions. Various mesoporous materials such as MCM-41, MCM-48, SBA-15 and SBA-16 have been reported in past two decades. Synthesis of mesoporous materials involves the concept of aggregation of surfactants as structure directing agents under acidic or basic conditions. The dimensions of these mesopores can be obtained by type of surfactant, auxiliary chemicals and synthesis conditions. At present, SBA-15 has attracted more attention among different mesoporous silica structures due to their desirable properties such as thick pore wall and hexagonal mesopores (4–12 nm), high surface area, ease of synthesis and functionalization and high thermal and mechanical stability. In last few years, great effort has been made on the development of various methods for the synthesis of mesoporous materials as support for oxidation reactions. The aim of this review article is to focus mainly on mesoporous SBA-15 together with its application as support for various oxidation reactions.     

非硅系介孔材料及其应用

介孔材料孔容存贮高、表面凝缩特性优良,在光、电、磁、传感、催化等领域有着广阔的应用,是近年来国内外跨学科研究的热点。文章介绍了近几年来国际上颇为关注的非硅系介孔材料的主要研究动向及其应用方面的最新成果,内容包括介孔铝磷酸盐(AlPOs)、介孔碳、介孔金属氧化物等。     

Synthesis and properties of novel functional mesoporous materials

Structurally well-defined mesoporous materials with large surface area and homogeneous pore diameters have been intensively investigated in recent years, furthermore, organofunctionalized mesoporous materials have attracted much attention for their potential application in many fields, such as separation, adsorption and drug delivery. In this paper, fluorescent mesoporous materials were successfully synthesized through “Grafting” method by mesoporous materials and silicon nanocrystals. A comprehensive multi-analytical characterization of the structural and optical properties of the fluorescent materials was carried by fourier transform infrared spectroscopy, powder X-ray diffraction, nitrogen adsorption–desorption measurements, scanning electron microscopy and transmission electron microscope. The behavior of loading and release to ibuprofen has been tested. The fluorescent materials which integrated with two functional components displayed potential in optoelectronic and biomedical applications.