Mesostructured germanium with cubic pore symmetry

Regular mesoporous oxide materials have been widely studied and have a range of potential applications, such as catalysis, absorption and separation. They are not generally considered for their optical and electronic properties. Elemental semiconductors with nanopores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms. Here we describe cubic mesostructured germanium, MSU-Ge-1, with gyroidal channels containing surfactant molecules, separated by amorphous walls that lie on the gyroid (G) minimal surface as in the mesoporous silica MCM-48 (ref. 2). Although Ge is a high-melting, covalent semiconductor that is difficult to prepare from solution polymerization, we succeeded in assembling a continuous Ge network using a suitable precursor for Ge(4-) atoms. Our results indicate that elemental semiconductors from group 14 of the periodic table can be made to adopt mesostructured forms such as MSU-Ge-1, which features two three-dimensional labyrinthine tunnels obeying Ia3d space group symmetry and separated by a continuous germanium minimal surface that is otherwise amorphous. A consequence of this new structure for germanium, which has walls only one nanometre thick, is a wider electronic energy bandgap (1.4 eV versus 0.66 eV) than has crystalline or amorphous Ge. Controlled oxidation of MSU-Ge-1 creates a range of germanium suboxides with continuously varying Ge:O ratio and a smoothly increasing energy gap.     

An ordered mesoporous organosilica hybrid material with a crystal-like wall structure

Surfactant-mediated synthesis strategies are widely used to fabricate ordered mesoporous solids in the form of metal oxides, metals, carbon and hybrid organosilicas. These materials have amorphous pore walls, which could limit their practical utility. In the case of mesoporous metal oxides, efforts to crystallize the framework structure by thermal and hydrothermal treatments have resulted in crystallization of only a fraction of the pore walls. Here we report the surfactant-mediated synthesis of an ordered benzene-silica hybrid material; this material has an hexagonal array of mesopores with a lattice constant of 52.5 A, and crystal-like pore walls that exhibit structural periodicity with a spacing of 7.6 A along the channel direction. The periodic pore surface structure results from alternating hydrophilic and hydrophobic layers, composed of silica and benzene, respectively. We believe that this material is formed as a result of structure-directing interactions between the benzene-silica precursor molecules, and between the precursor molecules and the surfactants. We expect that other organosilicas and organo-metal oxides can be produced in a similar fashion, to yield a range of hierarchically ordered mesoporous solids with molecular-scale pore surface periodicity.     

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.     

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.     

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.     

有序介孔材料的合成及其在环境科学中的应用

有序介孔材料具有高比表面积，孔道排列长程有序，孔径在2－50nm之间。该类材料是以表面活性剂作为模板，在一定条件下模板与无机组分相互作用通过超分子组装过程形成的。人们已经合成出具有不同组成，孔结构和性能的介孔材料，这类材料在光，电，磁催化和吸附分离等许多领域有潜在应用价值。本文对介孔材料的合成，合成机理以及在环境科学中的应用进行了综述。     

SBA-15基功能材料吸附应用研究进展

介孔SBA-15分子筛因具有较大的孔径、较高的比表面积和较厚的孔壁,在催化、吸附、分离、药物控释以及化学传感等领域得到广泛的应用。介绍了介孔分子筛的发展过程,并着重就SBA-15基功能材料在吸附应用方面的研究状况进行概述,最后展望了SBA-15功能材料未来的发展方向与应用前景。     

具有核壳结构的金属有机框架纳米材料的研究进展

多组分无机纳米粒子(NPs)和金属有机框架(MOFs)的可控一体化,正在引领着多种新型多功能材料的形成.具有核壳结构的金属有机框架纳米粒子(NP@MOF),综合了多组分无机纳米粒子和金属有机框架(MOFs)协同性质,NP@MOF材料的突出优点是:它的组成具有无限选择性、壳上孔径具有可调性、核壳具有多功能性,这种突出的独特功能使得人们争相洞察其未来发展.主要综述了具有核壳结构的多组分金属有机框架纳米粒子的制备方法和研究进展,最后介绍了其在多相催化、气体存储等方面的应用.     

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.     

磁性介孔碳复合材料的制备与应用研究进展

磁性介孔碳复合材料兼具介孔碳材料和磁性材料的双重优势,不仅具备较高的比表面积、均一的孔径分布和环境友好等特点,而且还具有良好的磁性分离特性.首先介绍了介孔碳和磁性纳米粒子常见的制备方法,在此基础上重点综述了磁性介孔碳复合材料的制备方法,并比较了各种方法的优缺点,对磁性介孔碳复合材料在生物医药、催化和污水处理等领域的最新应用进行了概述,并展望了其未来的发展趋势.同时,探讨了环境友好的绿色合成路线在磁性介孔碳复合材料方面的优势和挑战.     

The structure and chemistry of the TiO(2)-rich surface of SrTiO(3) (001)

Oxide surfaces are important for applications in catalysis and thin film growth. An important frontier in solid-state inorganic chemistry is the prediction of the surface structure of an oxide. Comparatively little is known about atomic arrangements at oxide surfaces at present, and there has been considerable discussion concerning the forces that control such arrangements. For instance, one model suggests that the dominant factor is a reduction of Coulomb forces; another favours minimization of 'dangling bonds' by charge transfer to states below the Fermi energy. The surface structure and properties of SrTiO(3)--a standard model for oxides with a perovskite structure--have been studied extensively. Here we report a solution of the 2 x 1 SrTiO(3) (001) surface structure obtained through a combination of high-resolution electron microscopy and theoretical direct methods. Our results indicate that surface rearrangement of TiO(6-x) units into edge-sharing blocks determines the SrO-deficient surface structure of SrTiO(3). We suggest that this structural concept can be extended to perovskite surfaces in general.     

具有多相催化性能的金属有机框架的研究进展

相比传统的多孔碳和无机沸石材料,金属-有机骨架(MOFs)具有制备方便、易于修饰、高孔隙率、比表面积大、框架规模大小可调等优点,在气体存储、吸附分离、多相催化、磁学等广泛应用.文章结合作者实验室的研究,介绍了MOFs作为多相催化剂所具有的独特特点;评估了MOFs作为催化剂的潜力,重点从MOFs的结构要素出发总结了MOFs作为多相催化剂的应用现状;讨论了MOFs作为多相催化剂需要重视的问题,为定向合成此类材料在催化方面的应用提供基础和理论价值.     

Visualizing single-molecule diffusion in mesoporous materials

Periodic mesoporous materials formed through the cooperative self-assembly of surfactants and framework building blocks can assume a variety of structures, and their widely tuneable properties make them attractive hosts for numerous applications. Because the molecular movement in the pore system is the most important and defining characteristic of porous materials, it is of interest to learn about this behaviour as a function of local structure. Generally, individual fluorescent dye molecules can be used as molecular beacons with which to explore the structure of--and the dynamics within--these porous hosts, and single-molecule fluorescence techniques provide detailed insights into the dynamics of various processes, ranging from biology to heterogeneous catalysis. However, optical microscopy methods cannot directly image the mesoporous structure of the host system accommodating the diffusing molecules, whereas transmission electron microscopy provides detailed images of the porous structure, but no dynamic information. It has therefore not been possible to 'see' how molecules diffuse in a real nanoscale pore structure. Here we present a combination of electron microscopic mapping and optical single-molecule tracking experiments to reveal how a single luminescent dye molecule travels through linear or strongly curved sections of a mesoporous channel system. In our approach we directly correlate porous structures detected by transmission electron microscopy with the diffusion dynamics of single molecules detected by optical microscopy. This opens up new ways of understanding the interactions of host and guest.     

络合水热法合成介孔SnO2简

二氧化锡（SnO2）作为一种n型宽禁带半导体氧化物材料,广泛用于有机物催化、固态电子器件和锂离子电池电极材料领域。介孔SnO2具有较大的比表面积和纳米级有序孔道,与周围介质之间存在更强的相互作用力,可提高其在气敏传感器、催化反应中的应用效率。本文以SnCl4·5H2O为锡源,P123为模板剂,采用络合水热法合成了具有金红石结构的介孔二氧化锡,并考察了pH值、表面活性剂和添加剂等因素对介孔结构形成的影响;采用X射线衍射、透射电镜、荧光光谱等手段综合分析了产物的结构、形貌、成分及光学性质。结果表明所制备的介孔SnO2具有蠕虫状孔结构,表面积大,孔径集中分布在2～8 nm。合成的样品具有良好的光学性能,在光学材料领域具有应用前景。     

可挥发性有机化合物废气治理技术及其新进展

从经济学的一般均衡理论角度,分析了政府对食品安全进行监管的有效边界和稳定的均衡条件。需求和供给分析表明,食品安全监管的供给和需求存在一个合理的度,也就是说当食品安全监管供给边界曲线的斜率绝对值大于食品安全监管需求边界曲线的斜率绝对值时,食品安全监管便达到动态稳定均衡。     

合成条件对介孔空心微球的形貌及结构的影响研究

介孔空心微球的合成对于获得优良的吸附剂, 催化剂和药物缓释剂具有十分重要的意义. 采用十二胺(DDA)为主模板剂, 聚乙二醇1000(PEG1000)为辅助模板剂, 成功地合成出了具有介孔孔壁的, 比表面积可高达951.23 m2/g 的空心二氧化硅微球. 考察了温度, 浓度, 溶剂等合成条件对合成的介孔空心微球的结构及形貌的影响, 实验结果表明合成温度及溶剂对合成的材料的结构及形貌具有显著的影响. 不同比例的醇水混合体系用做溶剂时, 可得到形貌及有序度完全不同的物质. 最佳的合成温度约为30-40℃, 低于该温度时, 合成的样品难以形成空心球结构, 而高于该温度时, 空心球结构将受到破坏. 此外, 模板剂的浓度也对合成样品的结构具有重要的影响.     

亚磷酸盐微孔化合物研究进展

 由于微孔材料独特的结构特点及在分离、吸附、离子交换和催化等方面的应用,探索合成具有新颖结构的微孔化合物成为当今研究的热点。磷酸盐分子筛是应用和研究最为广泛的一类微孔材料。亚磷酸盐微孔化合物作为磷酸盐分子筛材料的延伸,近年来引起科学家的极大兴趣。人们致力于合成具有大孔、螺旋、手性骨架等新颖结构的亚磷酸盐系列化合物,在很大程度上推动了微孔化合物的研究。目前,亚磷酸盐微孔化合物的研究已经涉及到元素周期表中的大部分金属元素,合成方法多样,所用模板剂种类繁多。通过对不同金属亚磷酸盐的综述,总结了亚磷酸盐化合物的结构特点、合成方法及模板剂在化合物合成中所起的作用,并介绍了其最新研究进展。     

孔径可调介孔La-Co-Ce-O系复合氧化物的制备

采用有机模板剂去除法制备介孔La-Co-Ce-O系复合氧化物,研究溶液体系的pH值及模板剂十六烷基三甲基溴化铵(CTAB)浓度对晶态和孔径结构影响;对制备的样品采用XRD测试和N2吸脱附方法表征其晶态结构和孔径结构。研究结果表明:该介孔氧化物具有较高的比表面积(高达160m2/g)和均匀的孔径;当pH值和CTAB浓度变化时,实现介孔La-Co-Ce-O系复合氧化物的孔径在3.0～21.0nm之间可调;制备条件的变化对介孔氧化物样品的晶态结构稍有影响。     

High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings

Crystalline molecular sieves with large pores and high adsorption capacities have many potential applications. Of these materials, zeolites are of particular interest owing to their stability in a wide range of experimental conditions. An aluminophosphate with very large circular channels(5) containing 18 oxygen atoms (18-ring channels) has been synthesized, but in the search for large-pore zeolites, most of the materials which have been synthesized up to now contain only 14-ring channels; the synthesis of zeolites with larger ring structures has been believed to be hindered by the low Si-O-Si bond angles available. A silicogaloaluminate (ECR-34) with unidirectional 18-ring channels was recently reported, but exhibited low micropore volume, thus rendering the material less attractive for catalytic applications. Here we report the structure and catalytic activity of the silicogermanate zeolite ITQ-33; this material exhibits straight large pore channels with circular openings of 18-rings along the c axis interconnected by a bidirectional system of 10-ring channels, yielding a structure with very large micropore volume. The conditions for synthesis are easily accessible, but are not typical, and were identified using high-throughput techniques.     

Crystalline mesoporous metal oxide

Since the discovery of many types of mesoporous silicas, such as SBA-15, KIT-6, FDU-12 and SBA-16, porous crystalline transition metal oxides, such as Cr2O3, Co3O4, In2O3, NiO, CeO2, WO3, Fe2O3 and MnO2, have been synthesized using the mesoporous silicas as hard templates. Several synthetic methods have been developed. These new porous materials have high potential applications in catalysis, Li-ion rechargeable batteries and gas sensors. This article gives a brief review of the research of porous crystals of metal oxides in the last four years.