Reticular synthesis and the design of new materials

The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.     

Free-standing mesoporous silica films with tunable chiral nematic structures

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.     

A homochiral metal-organic porous material for enantioselective separation and catalysis

Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.     

Synthesis and characterization of chiral mesoporous silica

Chirality is widely expressed in organic materials, perhaps most notably in biological molecules such as DNA, and in proteins, owing to the homochirality of their components (d-sugars and l-amino acids). But the occurrence of large-scale chiral pores in inorganic materials is rare. Although some progress has been made in strategies to synthesize helical and chiral zeolite-like materials, the synthesis of enantiomerically pure mesoporous materials is a challenge that remains unsolved. Here we report the surfactant-templated synthesis of ordered chiral mesoporous silica, together with a general approach for the structural analysis of chiral mesoporous crystals by electron microscopy. The material that we have synthesized has a twisted hexagonal rod-like morphology, with diameter 130-180 nm and length 1-6 micro m. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels of 2.2 nm diameter winding around the central axis of the rods. Our findings could lead to new uses for mesoporous silica and other chiral pore materials in, for example, catalysis and separation media, where both shape selectivity and enantioselectivity can be applied to the manufacturing of enantiomerically pure chemicals and pharmaceuticals.     

Reconfigurable self-assembly through chiral control of interfacial tension

From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil-water interfaces. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex topologies.     

A mesoporous germanium oxide with crystalline pore walls and its chiral derivative

Microporous oxides are inorganic materials with wide applications in separations, ion exchange and catalysis. In such materials, an important determinant of pore size is the number of M (where M = Si, Ge and so on) atoms in the rings delineating the channels. The important faujasite structure exhibits 12-ring structures while those of zeolites, germanates and other materials can be much larger. Recent attention has focused on mesoporous materials with larger pores of nanometre scale; however, with the exception of an inorganic-organic hybrid, these have amorphous pore walls, limiting many applications. Chiral porous oxides are particularly desirable for enantioselective sorption and catalysis. However, they are very rare in microporous and mesoporous materials. Here we describe a mesoporous germanium oxide, SU-M, with gyroidal channels separated by crystalline walls that lie about the G (gyroid) minimal surface as in the mesoporous MCM-48 (ref. 9). It has the largest primitive cell and lowest framework density of any inorganic material and channels that are defined by 30-rings. One of the two gyroidal channel systems of SU-M can be filled with additional oxide, resulting in a mesoporous crystal (SU-MB) with chiral channels.     

Direct imaging of the pores and cages of three-dimensional mesoporous materials

Mesostructured composite materials, with features ranging from 20 to 500 A in size, are obtained by the kinetically controlled competitive assembly of organic and inorganic species into nanostructured domains. Short-range order is limited, and long-range order is determined by weak forces such as van der Waals or hydrogen-bonding. Three-dimensional mesoporous materials obtained by removing the organic phase are of particular interest for applications such as catalysis and chemical sensing or separation, for which structural features such as cavity shape, connectivity and ordered bimodal porosity are critical. But atomic-scale structural characterization by the usual diffraction techniques is challenging for these partially ordered materials because of the difficulty in obtaining large (> 10 microm) single crystals, and because large repeat spacings cause diffraction intensities to fall off rapidly with scattering angle so that only limited small-angle data are available. Here we present a general approach for the direct determination of three-dimensional mesoporous structures by electron microscopy. The structure solutions are obtained uniquely without pre-assumed models or parametrization. We report high-resolution details of cage and pore structures of periodically ordered mesoporous materials, which reveal a highly ordered dual micro- and mesoscale pore structure.     

不同分子量聚合物溶液在多孔介质中的渗流特性研究

通过岩心流动实验,探讨了部分水解聚丙烯酰胺溶液(HPAM)在多孔介质中流动时聚合物分子量和孔隙特征参数对流动行为的影响,得到了一组反映流动参数变化规律的关系曲线。结果表明,在消除黏度效应条件下,高分子量聚合物比低分子量聚合物降低水相渗透率的能力强;聚合物分子量越高,多孔介质渗透率越低,阻力系数和残余阻力系数越大,聚合物越早突破多孔介质;当平均孔隙半径与聚合物分子尺寸之比大于4时,多孔介质的孔隙通道一般不会发生聚合物堵塞.     

2-(4-吡啶基)咪唑二羧酸锌配位聚合物的自发拆分

非手性配体2-(4-吡啶基)-4,5-咪唑二羧酸（H2L）与硝酸锌进行水热反应得到组成为[ZnL]n?2nH2O的自发拆分的2种三维金属-有机框架手性晶体，空间群分别为P41212和P43212，其中配位多面体分别为和型Zn(NO)2N三角双锥结构. 两种晶体分别存在着约0. 2 nm宽的不同手性的超微四方孔道，容纳的结晶水分子通过氢键分别形成右手和左手螺旋. 320 ℃以下主体框架保持稳定. 晶体在440 nm左右的荧光发射相比配体增强2倍以上. 该研究对于由非手性原料合成手性多空材料的进一步研究具有积极意义.     

Recent advances in hydrogen storage technologies based on nanoporous carbon materials

Hydrogen is a promising energy carrier that can potentially facilitate a transition from fossil fuels to sustainable energy sources without producing harmful by-products. Prior to realizing a hydrogen economy, however, viable hydrogen storage materials must be developed. Physical adsorption in porous solids provides an opportunity for hydrogen storage under low-stringency conditions. Physically adsorbed hydrogen molecules are weakly bound to a surface and, hence, are easily released. Among the various surface candidates, porous carbons appear to provide efficient hydrogen storage, with the advantages that porous carbon is relatively low-cost to produce and is easily prepared. In this review, we summarize the preparation methods, pore characteristics, and hydrogen storage capacities of representative nanoporous carbons, including activated carbons, zeolite-templated carbon, and carbide-derived carbon. We focus particularly on a series of nanoporous carbons developed recently: metal–organic framework-derived carbons, which exhibit promising properties for use in hydrogen storage applications.     

Biomimetic self-templating supramolecular structures

In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials. During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures. A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres, distinctively coloured skin tissues from cholesteric phase fibre bundles, and mineralized tissues from hierarchically organized fibres. Nature's self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods. However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.     

毛竹与樟子松木材孔隙结构的比较

【目的】竹木材料孔隙结构特征是影响材料性能的重要因素。通过定量表征与直观观察相结合方式探索竹木材料内部孔隙结构特征。通过对比分析,建立竹木材料内部孔隙结构与组织构造的对应关系,分析竹木材料内部孔隙结构差异,研究孔隙结构对材料性能的影响。【方法】以毛竹和樟子松木材为试验材料,采用压汞法对材料的孔隙率、孔体积、孔径分布、比表面积等参数进行定量测试,分析材料的孔隙结构特征。采用扫描电镜对材料的组织结构(毛竹:导管、筛管、薄壁细胞和纹孔等部位。樟子松:管胞、射线薄壁细胞、纹孔等部位)进行观察,确定各组织结构所构成孔隙的孔径范围。【结果】孔隙率(毛竹47.58%、樟子松67.16%)及汞压入量(毛竹0.633 mL/g、樟子松1.596 mL/g)测试结果表明毛竹内部孔体积显著低于樟子松。总孔面积(毛竹82.04 m²/g、樟子松18.16 m²/g)及中孔孔径(毛竹33.8 nm、樟子松445.0 nm)对比结果表明毛竹中大部分孔隙集中在孔径较小区域(32.4 nm左右),而樟子松木材中孔隙孔径主要集中在226.7、7 082.3 nm左右,造成毛竹孔面积显著高于樟子松木材。结合扫描电镜观察结果可知,毛竹中孔径11.3～100 μm范围内孔隙主要对应导管、基本组织中的薄壁细胞及纤维细胞。而835.0 nm左右孔隙对应基本组织及纤维细胞上纹孔。樟子松木材中孔径20 μm左右孔隙对应樟子松木材管胞; 而7 082.3 nm左右孔隙则对应具缘纹孔的纹孔口和射线薄壁细胞。此外,毛竹和樟子松木材中孔径小于1 μm的孔隙结构(毛竹中32.4 nm左右,樟子松木材中226.7、749.9 nm左右)主要位于具缘纹孔塞缘及细胞壁上。【结论】采用压汞法和扫描电镜观察方法可以实现对毛竹及樟子松木材孔隙结构的表征分析,有助于分析竹木材料性能差异产生的原因。然而,在通过压汞测试材料孔隙结构参数时,受墨水瓶孔效应影响,部分孔径较大的孔隙被认为是小孔,影响测试结果的准确性。因此,后续研究应考虑竹木材料的孔隙形态,从而实现对竹木材料孔隙结构的全面准确表征。     

共价有机框架的合成及其在生物医学领域应用研究进展

共价有机框架（COFs）作为一类由热力学稳定的共价键连接在一起的结晶型多孔有机聚合物材料,具有稳定性高、比表面积大、孔隙率大、晶体结构高度有序、化学物理性质可控等优良特性,已经在化学和能源等领域展现出巨大的应用价值.近年来,研究者们探索了COFs在生物医学方面的应用,并引发了广泛的关注.文章对于常用的COFs合成方法及其在生物医学领域的应用进行了总结,重点介绍了COFs在生物传感以及肿瘤治疗方面的应用进展.此外,还讨论了该领域面临的挑战及未来发展方向.     

A titanosilicate molecular sieve with adjustable pores for size-selective adsorption of molecules

Zeolites and related crystalline microporous oxides-tetrahedrally coordinated atoms covalently linked into a porous framework-are of interest for applications ranging from catalysis to adsorption and ion-exchange. In some of these materials (such as zeolite rho) adsorbates, ion-exchange, and dehydration and cation relocation can induce strong framework deformations. Similar framework flexibility has to date not been seen in mixed octahedral/tetrahedral microporous framework materials, a newer and rapidly expanding class of molecular sieves. Here we show that the framework of the titanium silicate ETS-4, the first member of this class of materials, can be systematically contracted through dehydration at elevated temperatures to 'tune' the effective size of the pores giving access to the interior of the crystal. We show that this so-called 'molecular gate' effect can be used to tailor the adsorption properties of the materials to give size-selective adsorbents suitable for commercially important separations of gas mixtures of molecules with similar size in the 4.0 to 3.0 A range, such as that of N2/CH4, Ar/O2 and N2/O2.     

微孔有机聚合物

微孔有机聚合物是一种新型的多孔材料,在非均相催化、吸附、分离和气体存储等方面具有潜在的应用.它是最近几十年发展起来的,全部由有机分子的构建块组装而成的微孔（孔径小于2.0nm）固体.依据设计策略的不同,主要可以分成以下4种：（1）通过交联反应阻止链密堆积的超交联聚合物;（2）通过刚性和扭曲基团阻止链密堆积的自具微孔聚合物;（3）通过大共轭？-体系刚性结构组建的共轭微孔聚合物;（4）通过适宜的官能团发生可逆地缩合反应来制备的共价有机骨架聚合物.本文根据国内外的研究背景,重点介绍自具微孔聚合物和共轭微孔聚合物.     

溶胶-凝胶技术制备纳米材料的研究进展

溶胶－凝胶技术是制备纳米材料的特殊工艺,工艺简单,易于操作。笔对溶胶－凝胶技术的基本过程、工艺特点进行了分析,从溶胶－凝胶技术在薄膜方面的应用、膜板合成纳米阵列,以及制备纳米复合材料等方面,对溶胶－凝胶技术制备纳米材料的研究状况进行了详尽阐述。     

SDS对ZnO多孔纳米块体孔道结构的影响

以ZnO纳米颗粒为原料，十二烷基硫酸钠（SDS）水溶液作造孔剂，利用我们独有的液态溶剂热压方法制备了ZnO多孔纳米块体. 实验结果表明，通过调控SDS溶液的浓度,可以调节ZnO多孔纳米块体的结构参数. 当SDS的浓度达到4.34×10^-1mol/L时，ZnO多孔纳米块体的孔道空间分布均匀性最好，孔径分布也最窄. 另外，红外分析结果表明，在液态溶剂热压制备ZnO多孔纳米块体过程中，SDS在ZnO多孔纳米块体的孔道中有微量残留.     

圆柱形空腔多孔材料辐射效应研究

 多孔材料具有孔隙率高、密度小和比表面积大等特征,在消声、减震、隔热和电磁屏蔽等应用方面具备多种优异性能。由于其在气孔中存在低热导率的空气介质,可以用作绝热材料。与其他相应材料相比,它具有耐高温和强度高的优点,已被广泛应用于航空航天、原子能和交通运输等行业。本文研究了热辐射效应对圆柱形空腔多孔材料传热性能的影响,推导了多孔材料局部有效热导率的方便工程应用的封闭公式。与已有理论结果比较,给出了本文公式的精度。数值算例揭示了孔洞对于热传输的有意义的影响规律。多孔材料的局部有效热导率可以分为两部分：一部分由固相和气相的纯传导引起,无量纲化的传导热导率不依赖于温度和孔径;另一部分由热辐射引起,随温度和孔径的变化而剧烈变化。在温度较低和孔径较小的情形下,辐射影响可以忽略不计。     

Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica

Since the discovery of MCM-41 more than ten years ago, many investigations have explored the suitability of hexagonal mesoporous silicas for potential practical applications. These range from catalysis and optically active materials to polymerization science, separation technology and drug delivery, with recent successes in the fabrication of hybrid mesoporous organosilicas expected to open up further application possibilities. Because the pore voids of this class of materials exhibit relatively narrow pore size distributions in the range of 2-4 nm in diameter, mesoporous silicas can selectively include organic compounds and release them continuously at a later stage. The functionalization of MCM-41 pore voids with photoactive derivatives provides influence over the material's absorption behaviour, but full control over the release process remains difficult. Here we show that the uptake, storage and release of organic molecules in MCM-41 can be regulated through the photocontrolled and reversible intermolecular dimerization of coumarin derivatives attached to the pore outlets. Successful functionalization requires uncalcined MCM-41 still filled with the template molecules that directed the formation of its pores, to ensure that coumarin derivatives attach preferentially to the pore outlets, rather than their inside walls. We find that this feature and the one-dimensional, isolated nature of the individual pores allow for efficient and reversible photocontrol over guest access to the material's interior.     

Varied pore organization in mesostructured semiconductors based on the [SnSe4](4-) anion

Open framework metal chalcogenide solids, with pore sizes in the nano- and mesoscale, are of potentially broad technological and fundamental interest in research areas ranging from optoelectronics to the physics of quantum confinement. Although there have been significant advances in the design and synthesis of mesostructured silicas, the construction of their non-oxidic analogues still remains a challenge. Here we describe a synthetic strategy that allows the preparation of a large class of mesoporous materials based on supramolecular assembly of tetrahedral Zintl anions [SnSe4]4- with transition metals in the presence of cetylpyridinium (CP) surfactant molecules. These mesostructured semiconducting selenide materials are of the general formulae (CP)4-2xMxSnSe4 (where 1.0 < x < 1.3; M=Mn, Fe, Co, Zn, Cd, Hg). The resulting materials are open framework chalcogenides and form mesophases with uniform pore size (with spacings between 35 and 40 A). The pore arrangement depends on the synthetic conditions and metal used, and include disordered wormhole, hexagonal and even cubic phases. All compounds are medium bandgap semiconductors (varying between 1.4 and 2.5 eV). We expect that such semiconducting porous networks could be used for optoelectronic, photosynthetic and photocatalytic applications.