有序介孔硅胶及其复合材料作固定相在液相色谱中的应用

系统地介绍了有序介孔硅胶及其复合材料的研究进展。重点评述了颗粒状无机介孔硅胶材料、颗粒状有机-无机复合介孔硅胶材料、手性介孔硅胶材料和整块介孔硅胶材料在用作液相色谱固定相方面的最新进展。对硅基有序介孔材料制备方面存在的问题进行了分析,并就该领域今后的发展趋势做了展望。     

Mini Review: Electroanalytical Sensors of Mesoporous Silica Materials

Mesoporous silica materials are promising substrates for electroanalytical sensors and electrocatalysis. Their characteristics include uniform pore sizes, surface areas in excess of 1000 m² g^?1, and long-range ordering of the packing of pores. The size scale, aspect ratio, and properties of mesoporous silica provide advantages in a variety of sensor applications. To improve performance, miniaturize platforms, and expand applications for trace analysis, novel materials with high sensitivity and rapid response have been developed and employed in recent years. These materials include pure mesoporous silica, mesoporous silica functionalized with organic groups, and composite or hybrid mesoporous silica. In this review, recent advances are outlined involving the application of mesoporous silica-based materials in electroanalytical sensors.     

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc.     

Medical applications of organic-inorganic hybrid materials within the field of silica-based bioceramics

Research on bioceramics has evolved from the use of inert materials for mere substitution of living tissues towards the development of third-generation bioceramics aimed at inducing bone tissue regeneration. Within this context hybrid bioceramics have remarkable features resulting from the synergistic combination of both inorganic and organic components that make them suitable for a wide range of medical applications. Certain bioceramics, such as ordered mesoporous silicas, can exhibit different kind of interaction with organic molecules to develop different functions. The weak interaction of these host matrixes with drug molecules confined in the mesoporous channels allows these hybrid systems to be used as controlled delivery devices. Moreover, mesoporous silicas can be used to fabricate three (3D)-dimensional scaffolds for bone tissue engineering. In this last case, different osteoinductive agents (peptides, hormones and growth factors) can be strongly grafted to the bioceramic matrix to act as attracting signals for bone cells to promote bone regeneration process. Finally, recent research examples of organic-inorganic hybrid bioceramics, such as stimuli-responsive drug delivery systems and nanosystems for targeting of cancer cells and gene transfection, are also tackled in this tutorial review (64 references).     

A Single‐Step Synthesis of Electroactive Mesoporous ProDOT‐Silica Structures

The single‐step preparation of highly ordered mesoporous silica hybrid nanocomposites with conjugated polymers was explored using a novel cationic 3,4‐propylenedioxythiophene (ProDOT) surfactant (PrS). The method does not require high‐temperature calcination or a washing procedure. The combination of self‐assembly of the silica surfactant and in situ polymerization of the ProDOT tail is responsible for creation of the mesoporosity with ultralarge pores, large pore volume, and electroactivity. As this novel material exhibits excellent textural parameters together with electrical conductivity, we believe that this could find potential applications in various fields. This novel concept of creating mesoporosity without a calcination process is a significant breakthrough in the field of mesoporous materials and the method can be further generalized as a rational preparation of various mesoporous hybrid materials having different structures and pore diameters.     

Vitalising porous inorganic silica networks with organic functions--PMOs and related hybrid materials

Mesoporous organic-inorganic hybrid materials are an interesting class of materials, which combine the advantages of two worlds; the inorganic part builds a robust substrate while organic functions make them alive in a way that they can be potentially used in a number of applications. In this tutorial review, we provide an overview of how mesoporous materials are synthesised via the 'soft template' path and how the incorporation of organic functions can be achieved. Furthermore, a colourful survey full of examples is presented, providing a small overview of field of applications that can potentially benefit from the use of periodic mesoporous organosilicas (PMOs) and related materials.     

介孔气体吸附剂

介孔二氧化硅经过表面修饰,赋予介孔材料不同的特性,具有很多的潜在用途,是无机材料研究的热点之一。本文综述了近年来以介孔二氧化硅（M41S 和 SBA）为载体设计的气体吸附剂的研究进展。详细讨论了二氧化碳和可挥发性有机物(VOCs)在介孔吸附剂上的吸附过程;介绍了二氧化碳介孔吸附剂的不同制备方法和影响二氧化碳在介孔吸附剂上吸附的因素,以及介孔吸附剂的结构对可挥发性有机物吸附过程的影响。最后,对介孔气体吸附剂的发展进行了展望。     

介孔硅材料及其负载型催化剂去除挥发性有机物的最新进展

介孔硅材料由于具有大的比表面积,均一的孔结构和大的孔径,常被用于分离、吸附和催化等领域.本文综述了近年来国内外介孔硅材料及其负载型催化剂去除各类挥发性有机物(VOCs)的研究进展,主要包括烃类、甲醇、甲醛、丙酮、苯、甲苯、萘、乙酸乙酯等.讨论了介孔硅材料的结构对VOCs吸附过程的影响;介绍了不同催化剂消除各类VOCs的催化性能及反应机理,并重点评述了甲苯在不同催化剂上的研究进展.分析结果表明,介孔硅材料的表面环境、孔道结构以及宏观形貌是影响VOCs分子在介孔硅材料上吸附的主要因素;贵金属催化剂的应用需要提高其抗中毒性以及降低成本;过渡金属的研究应着重于研发高活性的负载型过渡金属复合氧化物催化剂.最后对国内外介孔硅材料及其负载型催化剂的发展进行了展望,今后催化剂的设计可以从“氧化硅载体”和“介孔孔道”两个方面展开,这将为设计合适的催化剂处理各类VOCs污染物提供一定参考.     

Manipulation of molecular transport into mesoporous silica thin films by the infiltration of polyelectrolytes

The design of hybrid mesoporous materials incorporating polymeric assemblies as versatile functional units has become a very fertile research area offering major opportunities for controlling molecular transport through interfaces. However, the creation of such functional materials depends critically on our ability to assemble polymeric units in a predictable manner within mesopores with dimensions comparable to the size of the macromolecular blocks themselves. In this work, we describe for the first time the manipulation of the molecular transport properties of mesoporous silica thin films by the direct infiltration of polyelectrolytes into the inner environment of the 3D porous framework. The hybrid architectures were built up through the infiltration-electrostatic assembly of polyallylamine (PAH) on the mesopore silica walls, and the resulting systems were studied by a combination of experimental techniques including ellipso-porosimetry, cyclic voltammetry and X-ray photoelectron spectroscopy, among others. Our results show that the infiltration-assembly of PAH alters the intrinsic cation-permselective properties of mesoporous silica films, rendering them ion-permeable mesochannels and enabling the unrestricted diffusion of cationic and anionic species through the hybrid interfacial architecture. Contrary to what happens during the electrostatic assembly of PAH on planar silica films (quantitative charge reversal), the surface charge of the mesoporous walls is completely neutralized upon assembling the cationic PAH layer (i.e., no charge reversal occurs). We consider this work to have profound implications not only on the molecular design of multifunctional mesoporous thin films but also on understanding the predominant role of nanoconfinement effects in dictating the functional properties of polymer-inorganic hybrid nanomaterials.     

Synthesis of multifunctional metal- and metal oxide core@mesoporous silica shell structures by using a wet chemical approach

We demonstrate a facile wet chemical approach for fabricating spherical metal/metal-oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO(2) ) shells were fabricated over the pre-synthesized spherical SiO(2) nanoparticles through a three-step strategy: 1)?synthesis of core materials, 2)?covering the core with an organic-inorganic composite layer, and 3)?removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO(2) , into the pores of an mSiO(2) shell. Mn and TiO(2) cluster- incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero-element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications.     

Fabrication and analytical applications of hybrid mesoporous membranes.

Recently, a hybrid mesoporous membrane composed of surfactant-templated mesoporous silica inside a porous anodic alumina membrane has been developed. Since this membrane allows the use of columnar silica-mesopores (silica-nanochannels) as nanofluidic channels, separation of molecules can be realized by mass transport through the silica-nanochannel with molecular dimensions. Here, we review the methods to fabricate the hybrid mesoporous membranes, their structural features, and the analytical applications of hybrid mesoporous membranes.     

共价键联的多金属氧酸盐/SBA-15介孔杂化材料的电化学性质研究

采用循环伏安法和碳糊电极, 考察了用共缩合法和二次嫁接法合成的多金属氧酸盐(POM)/SBA-15介孔杂化材料的电化学性质以及氧化还原性能. 在乙腈介质和所检测的电势范围内, 溶液中游离的 物种和浸渍负载于介孔氧化硅上的同样POM物种显示两对W^VI单电子氧化还原峰; 共价键联于介孔氧化硅上的 物种也显示两对峰, 但第一对峰的峰电流增大, 还原电位比浸渍样品正移, 表明共价键联的POM不仅能够保持其原有的氧化还原性能, 而且比浸渍负载的POM具有更强的氧化性. 峰流～扫速的关系显示, 在低扫速时, 样品的氧化还原过程是表面控制的; 在高扫速时, 则是扩散控制的. 另外, 钨磷酸盐样品的氧化性大于钨硅酸盐样品; 共缩合法和二次嫁接法合成的样品具有相似的电化学行为.     

Functional-template directed self-assembly (FTDSA) of mesostructured organic-inorganic hybrid materials

Since the discovery of a surfactant directed self-assembly approach for the fabrication of mesoporous silica in 1992, increasing attention has been focused on the design and synthesis of mesostructured functional materials. Organic functionalization is becoming a major topic in this research field, since highly ordered mesostructured organic-inorganic hybrids offer novel functionalities and enhanced performance over their individual components. We begin with a brief overview of the three fundamental methods (post-synthetic grafting technique, co-condensation method, and preparation of periodic mesoporous organosilicas) for the preparation of organically functionalized mesostructured silica, and focus on one of the most promising approaches, which herein was named as functional-template directed self-assembly (FTDSA) approach, and in the eyes of the authors it has a special position in the preparation of this class of hybrid materials. A comprehensive overview of the state of research in the area of FTDSA and its potential applications will be given.     

有机-无机杂化氧化硅基介孔材料

有机基团可以通过嫁接或共聚的方法引入到氧化硅基介孔材料的孔表面或材料的骨架中,形成表面结合型和桥键型两大类有机-无机杂化氧化硅基介孔材料.本文综述了有机-无机杂化氧化硅基介孔材料的最新研究进展,介绍了其合成方法、应用及潜在的应用领域,详细总结了目前已报道的有机-无机杂化氧化硅基介孔材料的种类,展望了桥键型有机-无机杂化氧化硅基介孔材料的发展及应用前景.     

Mesoporous Silica Layer: Preparation and Opportunity

Periodic mesoporous silicas, which were prepared from silica‐surfactant mesostructured materials, have been investigated for a wide range of application due to their very large surface area, high porosity, pore size uniformity and variation, periodic pore arrangement and possible pore surface modification, after the pioneering papers on the formation of mesoporous silicas (MCM‐41 and FSM‐16). Morphosyntheses from such macroscopic morphologies as bulk monolith and film to nanoscopic ones, nanoparticles and their stable suspension, make mesoporous materials more attractive for applications and detailed characterization. Mesoporous silicas have been studied initially for such applications as adsorbent and catalyst, and more recently, optical, electronic, and bio‐related applications have been investigated. This review summarizes the studies on mesoporous silica film to highlight the present status and future of the preparation, characterization and application of the mesoporous silica film.     

Lanthanide (Eu3+, Tb3+) Centered Mesoporous Hybrids with 1,3‐Diphenyl‐1,3‐Propanepione Covalently Linking SBA‐15 (SBA‐16) and Poly(methylacrylic acid)

1,3‐Diphenyl‐1,3‐propanepione (DBM)‐functionalized SBA‐15 and SBA‐16 mesoporous hybrid materials (DBM‐SBA‐15 and DBM‐SBA‐16) are synthesized by co‐condensation of modified 1,3‐diphenyl‐1,3‐propanepione (DBM‐Si) and tetraethoxysilane (TEOS) in the presence of Pluronic P123 and Pluronic F127 as a template, respectively. The as‐synthesized mesoporous hybrid material DBM‐SBA‐15 and DBM‐SBA‐16 are used as the first precursor, and the second precursor poly(methylacrylic acid) (PMAA) is synthesized through the addition polymerization reaction of the monomer methacrylic acid. These precursors then coordinate to lanthanide ions simultaneously, and the final mesoporous polymeric hybrid materials Ln(DBM‐SBA‐15)₃PMAA and Ln(DBM‐SBA‐16)₃PMAA (Ln=Eu, Tb) are obtained by a sol‐gel process. For comparison, binary lanthanide SBA‐15 and SBA‐16 mesoporous hybrid materials (denoted as Ln(DBM‐SBA‐15)₃ and Ln(DBM‐SBA‐16)₃) are also synthesized. The luminescence properties of these resulting materials are characterized in detail, and the results reveal that ternary lanthanide mesoporous polymeric hybrid materials present stronger luminescence intensities, longer lifetimes, and higher luminescence quantum efficiencies than the binary lanthanide mesoporous hybrid materials. This indicates that the introduction of the organic polymer chain is a benefit for the luminescence properties of the overall hybrid system. In addition, the SBA‐15 mesoporous hybrids show an overall increase in luminescence lifetime and quantum efficiency compared with SBA‐16 mesoporous hybrids, indicating that SBA‐15 is a better host material for the lanthanide complex than mesoporous silica SBA‐16.     

铁掺杂SBA-15基中孔材料的合成、表征及应用研究进展

综述了含铁SBA-15材料的合成、表征及其应用的研究进展,重点总结了介孔材料合成过程中不同铁物种的调控合成方法与鉴别手段.     

新型有机-无机杂化碱性介孔材料的合成——空间位阻对催化性能的影响

通过直接合成方法制备了2个二级胺功能化的SBA-15型有机-无机杂化碱性介孔材料. 粉末X射线衍射分析、氮气吸附-脱附和透射电镜表征表明, 合成的材料保持了SBA-15的有序介孔孔道结构, 而热重、红外光谱和元素分析表明有机功能团被成功引入. 在对硝基苯甲醛和丙酮的羟醛缩合反应中, 相对于一级胺功能化的材料, 二级胺功能化的SBA-15展示了极大改进的催化活性, 这可能是由于具有更大空间位阻效应的有机功能团的引入导致了碱性胺中心催化活性增强.     

Controlled loadings in a mesoporous material: click-on silica

Hybrid mesoporous SBA-15 silicas were synthesized directly with variable alkylazide loading representing 2-50% surface coverage. These hybrid silica materials retain the favorable physical attributes of the parent SBA-15 materials and allow efficient covalent attachment of ethynylated organic moieties through a copper catalyzed 3 + 2 Huisgen cycloaddition reaction. Three distinctly different examples are provided demonstrating the efficiency and robust nature of this attachment synthetic strategy. The direct syntheses provide predefined loadings of randomly distributed organics within the materials, from site-dense to site-isolated. Such control over loadings along with simply implemented analytic procedures should facilitate the translation of homogeneous chemistries to heterogeneous supports.     

Preparation and characterization of polyimide/mesoporous silica hybrid nanocomposites based on water-soluble poly(amic acid) ammonium salt

Recently, mesoporous silica was blended with polyimide to develop low dielectric constant (k) materials with improving mechanical and thermal properties of polyimide by utilizing both the nanoporous structure and silica framework. However, even the use of mesoporous silica did not show a significant decrease of k due to the phase segregation in between polyimide and the mesoporous silica materials. In this work, we attempted to prepare polyimide/mesoporous silica hybrid nanocomposites having relatively good phase mixing behavior by utilizing polyimide synthesized from a water soluble poly(amic acid) ammonium salt, which lead to low k up to 2.45. The thermal properties of polyimide were improved by adding mesoporous silicas. For this work, we have fabricated mesoporous silicas through surfactant-templated condensation of tetraethyl orthosilicate (TEOS). Pyromellitic dianhydride (PMDA)-4,4′-oxydianiline (ODA) polyimide was prepared from poly(amic acid) ammonium salt, which had been obtained by incorporating triethylamine (TEA) into PMDA-ODA poly(amic acid) in dimethylacetamide (DMAc), followed by thermal imidization.