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.     

有机—无机纳米复合材料研究进展

有机-无机纳米复合材料兼有无机和有机物的特点。溶胶-凝胶法、插层复合法、辐射合成法等无机纳米复合材料的制备方法均具有广泛的应用前景,今后的研究重点应着眼于提高其技术工艺的成熟性,利于工业化生产。     

有机-无机混合阳离子钙钛矿发光二极管研究进展

 有机-无机杂化钙钛矿具有制备方便、光学带隙可调、电荷传输性能优异等特性,正成为新一代革命性的半导体光电材料。随着研究的不断发展,钙钛矿材料的量子产率已经超过90%。材料合成的快速发展促进了其在光电子器件上的应用,包括太阳能电池、发光二极管、光电探测器和晶体管等。本文回顾了有机-无机混合阳离子钙钛矿发光二极管的最新研究进展,包括材料晶体结构、纳米晶合成过程、器件制备及其光电特性表征。有机-无机混合阳离子为高量子产率钙钛矿纳米晶的合成开辟了一种新的途径,同时也为制备高亮度、高效率发光二极管器件提供了新的思路。     

Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound

Crystal engineering--the planning and construction of crystalline supramolecular architectures from modular building blocks--permits the rational design of functional molecular materials that exhibit technologically useful behaviour such as conductivity and superconductivity, ferromagnetism and nonlinear optical properties. Because the presence of two cooperative properties in the same crystal lattice might result in new physical phenomena and novel applications, a particularly attractive goal is the design of molecular materials with two properties that are difficult or impossible to combine in a conventional inorganic solid with a continuous lattice. A promising strategy for creating this type of 'bi-functionality' targets hybrid organic/inorganic crystals comprising two functional sub-lattices exhibiting distinct properties. In this way, the organic pi-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and its derivatives, which form the basis of most known molecular conductors and superconductors, have been combined with molecular magnetic anions, yielding predominantly materials with conventional semiconducting or conducting properties, but also systems that are both superconducting and paramagnetic. But interesting bulk magnetic properties fail to develop, owing to the discrete nature of the inorganic anions. Another strategy for achieving cooperative magnetism involves insertion of functional bulky cations into a polymeric magnetic anion, such as the bimetallic oxalato complex [MnIICrIII(C2O4)3]-, but only insoluble powders have been obtained in most cases. Here we report the synthesis of single crystals formed by infinite sheets of this magnetic coordination polymer interleaved with layers of conducting BEDT-TTF cations, and show that this molecule-based compound displays ferromagnetism and metallic conductivity.     

高层间距、大比表面氧化硅柱层状钛铌酸盐介孔材料的制备

Recently, a new kind of inorganic porous material--pillared layered metal oxide was developed. Compared with traditional pillared clays and metal phosphates, this kind of pillared materials can provide more versatile structural and physical properties, which in turn will find     

Inorganic Nanoparticles Conjugated with Biofunctional Molecules

1 Results We have attempted to conjugate inorganic nanoparticles with biofunctional molecules.Recently we were quite successful in demonstrating that a two-dimensional inorganic compound like layered double hydroxide (LDH),and natural and synthetic clays can be used as gene or drug delivery carriers1-4.To the best of our knowledge,such inorganic vectors are completely new and different from conventionally developed ones such as viruses and cationic liposomes,those which are limited in certain cases of ap...     

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。     

基于二阶姜-泰勒效应(SOJT)的新型非线性光学晶体研究进展

新型无机二阶非线性光学晶体材料在光电子领域如频率变换、光调制、通信和信息处理等领域有着重要的应用,是材料研究的前沿方向之一。1998年以来,人们利用易于发生二阶姜-泰勒效应的离子--d⁰过渡金属离子(e.g. Mo⁶⁺,W⁶⁺,V⁵⁺,Nb⁵⁺,etc.)和含有非成键孤对电子(stereochemically active lone pair, SCALP, e.g. I⁵⁺, Te⁴⁺, Se⁴⁺, Sn²⁺, etc.)的阳离子,合成了大量具有非中心对称结构的化合物,其中许多显示出很强的倍频效应(>400×α-SiO2),是一类有应用前景的非线性光学晶体材料。本文将这些材料分成三类进行综述,即:只含一类二阶姜-泰勒离子(d⁰或SCALP)的化合物;同时包含两类二阶姜-泰勒离子的化合物以及包含二阶姜-泰勒离子和其他非中心对称基团(共轭π-硼酸盐体系、PO₄四面体和d¹⁰离子)的化合物。本文分别就新材料探索、单晶生长等综述了近10年来基于二阶姜-泰勒效应的非线性光学晶体材料的研究进展。     

Chevrel phase: A review of its crystal structure and electrochemical properties

Chevrel phase compounds have attracted increasing attention as electrochemical energy storage materials and electro-catalysts. Benefiting from their unique crystal structure, Chevrel phase compounds can not only function as the host structures for reversible intercalation of a broad range of cations, but also exhibit high catalytic activity in electrochemical reduction reactions. Here we provide an overview of recent progress in the development of Chevrel phase materials including new understand...     

Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge9(4-) cluster, a compound whose use in the synthesis of nanoscale materials is established. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.     

A combustion-free methodology for synthesizing zeolites and zeolite-like materials

Zeolites are mainly used for the adsorption and separation of ions and small molecules, and as heterogeneous catalysts. More recently, these materials are receiving attention in other applications, such as medical diagnosis and as components in electronic devices. Modern synthetic methodologies for preparing zeolites and zeolite-like materials typically involve the use of organic molecules that direct the assembly pathway and ultimately fill the pore space. Removal of these enclathrated species normally requires high temperature combustion that destroys this high cost component, and the associated energy release in combination with the formed water can be extremely detrimental to the inorganic structure. Here we report a synthetic methodology that avoids these difficulties by creating organic structure-directing agents (SDAs) that can be disassembled within the zeolite pore space to allow removal of their fragments for possible use again by reassembly. The methodology is shown for the synthesis of zeolite ZSM-5 using a SDA that contains a cyclic ketal group that is removed from the SDA while it is inside the zeolite without destruction of the inorganic framework. This approach should be applicable to the synthesis of a wide variety of inorganic and organometallic structures.     

纤维素气凝胶材料研究进展

 气凝胶是一种具有纳米孔洞结构的新型固体材料,具有低热导率、低折射指数和低电阻率等特点,在隔热保温、吸附催化和高性能电容器等方面具有广阔的应用前景。本文综述气凝胶发展的历史及气凝胶的制备方法和应用,探讨了纤维素气凝胶研发中存在的问题,展望了纤维素气凝胶的未来发展。     

A route to high surface area, porosity and inclusion of large molecules in crystals

One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas. Such materials are of critical importance to many applications involving catalysis, separation and gas storage. The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m2 g(-1) (ref. 2). Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m2 g(-1) (ref. 3). But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m2 g(-1) (refs 4-7). Despite this, no method of determining the upper limit in surface area for a material has yet been found. Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date. We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a new metal-organic framework with a surface area estimated at 4,500 m2 g(-1). This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules--attributes not previously combined in one material.     

无机介孔材料在第三代电化学生物传感器中的应用研究

无机介孔材料是一种孔直径在2,50nm的多孔材料。这种材料具有结构规则,机械性能高、化学和热能稳定性好等特点。近年来,随着材料合成技术的提高,不断有新型高负载能力和生物相容性好的介孔材料被开发出来。同时,实验表明,无机介孔材料是固载生物大分子的良好载体。利用无机介孔材料固载氧化还原蛋白质并结合其的直接电子转移,为我们提供了一种新的构建第三代生物传感器的方法。基于无机介孔材料的特点及氧化还原蛋白质的直接电子转移,所构建的第三代电化学生物传感器有望具有较传统电化学传感器更好的性能。将介孔材料分为二氧化硅基和非二氧化硅基2大类,描述了无机介孔材料在第三代电化学生物传感器中的应用。     

Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity

Creating a robust synthetic surface that repels various liquids would have broad technological implications for areas ranging from biomedical devices and fuel transport to architecture but has proved extremely challenging. Inspirations from natural nonwetting structures, particularly the leaves of the lotus, have led to the development of liquid-repellent microtextured surfaces that rely on the formation of a stable air-liquid interface. Despite over a decade of intense research, these surfaces are, however, still plagued with problems that restrict their practical applications: limited oleophobicity with high contact angle hysteresis, failure under pressure and upon physical damage, inability to self-heal and high production cost. To address these challenges, here we report a strategy to create self-healing, slippery liquid-infused porous surface(s) (SLIPS) with exceptional liquid- and ice-repellency, pressure stability and enhanced optical transparency. Our approach-inspired by Nepenthes pitcher plants-is conceptually different from the lotus effect, because we use nano/microstructured substrates to lock in place the infused lubricating fluid. We define the requirements for which the lubricant forms a stable, defect-free and inert 'slippery' interface. This surface outperforms its natural counterparts and state-of-the-art synthetic liquid-repellent surfaces in its capability to repel various simple and complex liquids (water, hydrocarbons, crude oil and blood), maintain low contact angle hysteresis (<2.5°), quickly restore liquid-repellency after physical damage (within 0.1-1 s), resist ice adhesion, and function at high pressures (up to about 680 atm). We show that these properties are insensitive to the precise geometry of the underlying substrate, making our approach applicable to various inexpensive, low-surface-energy structured materials (such as porous Teflon membrane). We envision that these slippery surfaces will be useful in fluid handling and transportation, optical sensing, medicine, and as self-cleaning and anti-fouling materials operating in extreme environments.     

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.     

Three-dimensional interconnected cobalt oxide-carbon hollow spheres arrays as cathode materials for hybrid batteries

Hierarchical porous metal oxides arrays is critical for development of advanced energy storage devices. Herein, we report a facile template-assisted electro-deposition plus glucose decomposition method for synthesis of multilayer CoO/C hollow spheres arrays. The CoO/C arrays consist of multilayer interconnected hollow composite spheres with diameters of ～350 nm as well as thin walls of ～20 nm. Hierarchical hollow spheres architecture with 3D porous networks are achieved. As cathode of high-rate hybrid batteries, the multilayer CoO/C hollow sphere arrays exhibit impressive enhanced performances with a high capacity (73.5 mAh g?1 at 2 A g?1), and stable high-rate cycling life (70 mAh g?1 after 12,500 cycles at 2 A g?1). The improved electrochemical performance is owing to the composite hollow-sphere architecture with high contact area between the active materials and electrolyte as well as fast ion/electron transportation path.     

Sorption of wastewater containing reactive red X-3B on inorgano-organo pillared bentonite

Bentonite is a kind of natural clay with good exchanging ability. By exchanging its interlamellar cations with various soluble cations, such as quaternary ammonium cations and inorganic metal ions, the properties of natural bentonite can be greatly improved. In this study, hexadecyltrimethylammonium bromide (HDTMA), CaCl₂, MgCl₂, FeCl₃, AlCl₃ were used as organic and inorganic pillared materials respectively to produce several kinds of Ca-, Mg-, Fe-, Al-organo pillared bentonites. Sorption of reactive red X-3B on them was studied to determine their potential application as sorbents in wastewater treatment. The results showed that these pillared bentonites had much improved sorption properties, and that the dye solutions’ pH value had some effect on the performance of these inorgano-organo pillared bentonites. Isotherms of reactive X-3B on these pillared bentonites suggested a Langmuir-type sorption mechanism.     

卤胺抗菌材料的研究和应用

卤胺类化合物是一类新型的抗菌剂,它有效地克服了传统抗茵剂在实际应用中的一些缺点,是一类具有杀茵速度快,杀菌效率高,储存稳定,抗茵功效可再生等优点的绿色环保型抗菌剂．近年来,一些新颖的带有键合基团的卤胺前置体已被成功地接枝到各种基体材料如棉纤维、硅胶、聚苯乙烯树脂、聚乙烯、聚氨酯等的表面来制备各种抗菌材料和产品．特别是大孔交联的高分子卤胺抗茵树脂产品Halopure及其相关技术的成功开发,开创了卤胺抗茵材料在饮用水消毒领域应用的新纪元．介绍了该类抗菌材料的抗菌机理、合成与制备方法以及在日常生活各领域中的广泛应用前景,并对其今后的发展趋势作了展望．     

基于生物细胞调控合成无机纳米材料的研究进展

细胞作为生物体结构和功能的基本单位,其内部可进行成千上万的生化反应.利用生物体细胞来调控合成纳米材料是一种新型的绿色合成方法,有着传统方法不可比拟的优点:如原料来源广、低毒、低能耗、反应温和可控、效率高,环境友好等.利用细胞调控合成得到的无机纳米材料富含蛋白质、脂类、多糖等生物物质,不仅可以避免颗粒间的团聚,而且具有独特的生物相容性.本文综述了生物细胞内外无机纳米材料的可控合成研究进展,并展望了基于细胞合成无机纳米材料的发展前景.