新能源领域的质子交换膜研究与应用进展

质子交换膜作为燃料电池和液流电池的关键材料之一,近二十年来得到世界各国科学家的广泛关注和深入研究,先后研究开发出含氟高分子类、碳氢聚合物类、芳香烃聚合物类,以及有机/无机杂化材料的质子交换膜.在总结归纳这一领域的研究成果基础上,结合本课题组在液流电池领域的质子交换膜研究进展,论述质子交换膜技术在新能源技术领域未来若干年的研究开发重大需求,展望质子交换膜材料设计与可能的绿色合成技术路线.     

Characterizing the hierarchical structures of bioactive sol-gel silicate glass and hybrid scaffolds for bone regeneration

Bone is the second most widely transplanted tissue after blood. Synthetic alternatives are needed that can reduce the need for transplants and regenerate bone by acting as active temporary templates for bone growth. Bioactive glasses are one of the most promising bone replacement/regeneration materials because they bond to existing bone, are degradable and stimulate new bone growth by the action of their dissolution products on cells. Sol-gel-derived bioactive glasses can be foamed to produce interconnected macropores suitable for tissue ingrowth, particularly cell migration and vascularization and cell penetration. The scaffolds fulfil many of the criteria of an ideal synthetic bone graft, but are not suitable for all bone defect sites because they are brittle. One strategy for improving toughness of the scaffolds without losing their other beneficial properties is to synthesize inorganic/organic hybrids. These hybrids have polymers introduced into the sol-gel process so that the organic and inorganic components interact at the molecular level, providing control over mechanical properties and degradation rates. However, a full understanding of how each feature or property of the glass and hybrid scaffolds affects cellular response is needed to optimize the materials and ensure long-term success and clinical products. This review focuses on the techniques that have been developed for characterizing the hierarchical structures of sol-gel glasses and hybrids, from atomic-scale amorphous networks, through the covalent bonding between components in hybrids and nanoporosity, to quantifying open macroporous networks of the scaffolds. Methods for non-destructive in situ monitoring of degradation and bioactivity mechanisms of the materials are also included.     

Preparation of Inorganic Materials Using Ionic Liquids

Conventional synthesis of inorganic materials relies heavily on water and organic solvents. Alternatively, the synthesis of inorganic materials using, or in the presence of, ionic liquids represents a burgeoning direction in materials chemistry. Use of ionic liquids in solvent extraction and organic catalysis has been extensively studied, but their use in inorganic synthesis has just begun. Ionic liquids are a family of non‐conventional molten salts that can act as templates and precursors to inorganic materials, as well as solvents. They offer many advantages, such as negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility for both organic and inorganic molecules, and much synthetic flexibility. In this Review, the use of ionic liquids in the preparation of several categories of inorganic and hybrid materials (i.e., metal structures, non‐metal elements, silicas, organosilicas, metal oxides, metal chalcogenides, metal salts, open‐framework structures, ionic liquid‐functionalized materials, and supported ionic liquids) is summarized. The status quo of the research field is assessed, and some future perspectives are furnished.     

Chemistry of Mesoporous Organosilica in Nanotechnology: Molecularly Organic–Inorganic Hybridization into Frameworks

Organic–inorganic hybrid materials aiming to combine the individual advantages of organic and inorganic components while overcoming their intrinsic drawbacks have shown great potential for future applications in broad fields. In particular, the integration of functional organic fragments into the framework of mesoporous silica to fabricate mesoporous organosilica materials has attracted great attention in the scientific community for decades. The development of such mesoporous organosilica materials has shifted from bulk materials to nanosized mesoporous organosilica nanoparticles (designated as MONs, in comparison with traditional mesoporous silica nanoparticles (MSNs)) and corresponding applications in nanoscience and nanotechnology. In this comprehensive review, the state‐of‐art progress of this important hybrid nanomaterial family is summarized, focusing on the structure/composition–performance relationship of MONs of well‐defined morphology, nanostructure, and nanoparticulate dimension. The synthetic strategies and the corresponding mechanisms for the design and construction of MONs with varied morphologies, compositions, nanostructures, and functionalities are overviewed initially. Then, the following part specifically concentrates on their broad spectrum of applications in nanotechnology, mainly in nanomedicine, nanocatalysis, and nanofabrication. Finally, some critical issues, presenting challenges and the future development of MONs regarding the rational synthesis and applications in nanotechnology are summarized and discussed. It is highly expected that such a unique molecularly organic–inorganic nanohybrid family will find practical applications in nanotechnology, and promote the advances of this discipline regarding hybrid chemistry and materials.     

When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures

van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on‐demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self‐assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design.     

Recent Advances of Using Hybrid Nanocarriers in Remotely Controlled Therapeutic Delivery

The development of hybrid biomaterials has been attracting great attention in the design of materials for biomedicine. The nanosized level of inorganic and organic or even bioactive components can be combined into a single material by this approach, which has created entirely new advanced compositions with truly unique properties for drug delivery. The recent advances in using hybrid nanovehicles as remotely controlled therapeutic delivery carriers are summarized with respect to different nanostructures, including hybrid host–guest nanoconjugates, micelles, nanogels, core–shell nanoparticles, liposomes, mesoporous silica, and hollow nanoconstructions. In addition, the controlled release of guest molecules from these hybrid nanovehicles in response to various remote stimuli such as alternating magnetic field, near infrared, or ultrasound triggers is further summarized to introduce the different mechanisms of remotely triggered release behavior. Through proper chemical functionalization, the hybrid nanovehicle system can be further endowed with many new properties toward specific biomedical applications.     

Directed Assembly of Hybrid Nanomaterials and Nanocomposites

Hybrid nanomaterials are molecular or colloidal‐level combinations of organic and inorganic materials, or otherwise strongly dissimilar materials. They are often, though not exclusively, anisotropic in shape. A canonical example is an inorganic nanorod or nanosheet sheathed in, or decorated by, a polymeric or other organic material, where both the inorganic and organic components are important for the properties of the system. Hybrid nanomaterials and nanocomposites have generated strong interest for a broad range of applications due to their functional properties. Generating macroscopic assemblies of hybrid nanomaterials and nanomaterials in nanocomposites with controlled orientation and placement by directed assembly is important for realizing such applications. Here, a survey of critical issues and themes in directed assembly of hybrid nanomaterials and nanocomposites is provided, highlighting recent efforts in this field with particular emphasis on scalable methods.     

有机/无机纳米复合质子交换膜的研究进展

通过有机/无机复合的方法可以得到聚合物电解质膜燃料电池(PEMFCs)中用的纳米复合质子交换膜,膜的工作温度、保水能力、机械强度、抗渗透性能和薄膜的综合性能都有大幅度的提高.本文评述了研究得较多的几类有机/无机纳米复合质子交换膜的性能特点及最新研究进展,提出了有机/无机复合质子导电薄膜材料的一些设计和制备原则.     

Towards understanding biomineralization: calcium phosphate in a biomimetic mineralization process

Abstract Biomineralization processes result in organic/inorganic hybrid materials with complex shapes, hierarchical structures, and superior material properties. Recent developments in biomineralization and biomaterials have demonstrated that calcium phosphate particles play an important role in the formation of hard tissues in nature. In this paper, current concepts in biomineralization, such as nano assembly, biomimetic shell structure, and their applications are introduced. It is confirmed experimentally that enamel- or bone-liked apatite can be achieved by oriented aggregations using nano calcium phosphates as starting materials. The assembly of calcium phosphate can be either promoted or inhibited by different biomolecules so that the kinetics can be regulated biologically. In this paper, the role of nano calcium phosphate in tissue repair is highlighted. Furthermore, a new, interesting result on biomimetic mineralization is introduced, which can offer an artificial shell for living cells via a biomimetic method.     

耐热有机/无机杂化材料的研究进展

耐热有机/无机杂化材料是一类通过化学作用或者物理作用将有机相和无机相在纳米级别上结合起来的具有优良热性能的材料,其集成了有机相和无机相的优点,具有优良的力学性能、耐热性、加工性、电性能等,在许多领域都显示出巨大的应用前景.按照该类杂化材料的组成进行分类,并以此为依据逐类介绍了耐热有机/无机杂化材料的研究进展.现有耐热有机/无机杂化材料的制备仍以共混或添加型为主,含硅和(或)硼元素及其衍生物的杂化材料具有优良的耐热性.     

Organic—inorganic hybrid materials

Composite materials formed by the combination of inorganic materials and organic polymers are attractive for the purpose of creating high-performance or high-functional polymeric materials. Of particular interest is the molecular level combination of two different components that may lead to new composite materials, termed ‘organic—inorganic hybrid materials’. Recently, new methods for preparing these hybrid materials have been reported. Some improvements of the properties or modifications of these materials have also been explored from the viewpoint of industrial applications.     

有机硅溶胶-凝胶防腐蚀涂层研究进展

有机硅溶胶-凝胶涂层是指以烷基烷氧基硅烷为前驱体通过溶胶-凝胶技术制备的涂层。有机硅是分子水平上的有机-无机杂化分子,因此有机硅溶胶-凝胶涂层兼具了有机材料和无机材料的性能,并且能通过合理的调控有机和无机成分来获得所需的性能。其热稳定、耐刮擦性与无机材料的结合性能明显高于普通的有机材料,柔韧性与有机材料的结合性能明显高于一般的无机涂层。近年来,这种新型的、具有特殊性能的涂层被广泛研究用来保护金属材料(如铝、铁、镁、铜基材料)。介绍了有机硅溶胶-凝胶涂层涉及的基本反应、硅烷在金属表面上的成键机理以及在不同金属上的应用等方面的研究进展,并展望了有机硅溶胶-凝胶涂层应用前景及未来的研究方向。     

Crafting Semiconductor Organic−Inorganic Nanocomposites via Placing Conjugated Polymers in Intimate Contact with Nanocrystals for Hybrid Solar Cells

Semiconductor organic?inorganic hybrid solar cells incorporating conjugated polymers (CPs) and nanocrystals (NCs) offer the potential to deliver efficient energy conversion with low‐cost fabrication. The CP‐based photovoltaic devices are complimented by an extensive set of advantageous characteristics from CPs and NCs, such as lightweight, flexibility, and solution‐processability of CPs, combined with high electron mobility and size‐dependent optical properties of NCs. Recent research has witnessed rapid advances in an emerging field of directly tethering CPs on the NC surface to yield an intimately contacted CP?NC nanocomposite possessing a well‐defined interface that markedly promotes the dispersion of NCs within the CP matrix, facilitates the photoinduced charge transfer between these two semiconductor components, and provides an effective platform for studying the interfacial charge separation and transport. In this Review, we aim to highlight the recent developments in CP?NC nanocomposite materials, critically examine the viable preparative strategies geared to craft intimate CP?NC nanocomposites and their photovoltaic performance in hybrid solar cells, and finally provide an outlook for future directions of this extraordinarily rich field.     

Integrative Approaches to Hybrid Multifunctional Materials: From Multidisciplinary Research to Applied Technologies

Achieving nanostructured or hierarchical hybrid architectures involves cross‐cutting synthetic strategies where all facettes of chemistry (organic, polymers, solid‐state, physical, materials chemistries, biochemistry, etc…?), soft matter and ingenious processing are synergistically coupled. These cross‐cutting approaches are in the vein of bio‐inspired synthesis strategies where the integration of different areas of expertise allows the development of complex systems of various shapes with perfect mastery at different size scales, composition, porosity, functionality, and morphology. These strategies coined “Integrative Chemistry” open a land of opportunities to create advanced hybrid materials with organic‐inorganic or bio‐inorganic character. These hybrid materials represent not only a new field of basic research where creative chemists can express themselves, but also, via their remarkable new properties and multifunctional nature, hybrids are allowing the emergence of innovative industrial applications in extremely diverse fields.     

Shaping Colloidal Rutile into Thermally Stable and Porous Mesoscopic Titania Balls

High crystallinity and controlled porosity are advantageous for many applications such as energy conversion and power generation. Despite many efforts in the last decades, the direct synthesis of organic–inorganic composite materials with crystalline transition metal oxides is still a major challenge. In general, molecules serve as inorganic precursors and heat treatment is required to convert as‐synthesized amorphous composites to stable crystalline materials. Herein, an alternative approach to the direct synthesis of crystalline polymer–metal oxide composites by using a spherical polyelectrolyte brush as the template system is presented. Pre‐synthesized electrostatically stabilized rutile nanocrystals that carry a positive surface charge are used as inorganic precursors. In this approach, the strong Coulomb interactions between anionic polyelectrolyte brush chains and cationic crystalline rutile colloids, whose surfaces are not capped and therefore reactive, are the key factors for the organic–inorganic crystalline composite formation. Stepwise calcination first under argon and followed with a second calcination in air lead to the complete removal of the polymer template without collapse and porous rutile balls are obtained. The results suggest that any colloids that carry a surface charge might serve as inorganic precursors when charged templates are used. It is expected that this hierarchical route for structuring oxides at the mesoscale is generally applicable.     

Emissive ZnO-graphene quantum dots for white-light-emitting diodes

Hybrid nanostructures combining inorganic materials and graphene are being developed for applications such as fuel cells, batteries, photovoltaics and sensors. However, the absence of a bandgap in graphene has restricted the electrical and optical characteristics of these hybrids, particularly their emissive properties. Here, we use a simple solution method to prepare emissive hybrid quantum dots consisting of a ZnO core wrapped in a shell of single-layer graphene. We then use these quantum dots to make a white-light-emitting diode with a brightness of 798?cd?m(-2). The strain introduced by curvature opens an electronic bandgap of 250?meV in the graphene, and two additional blue emission peaks are observed in the luminescent spectrum of the quantum dot. Density functional theory calculations reveal that these additional peaks result from a splitting of the lowest unoccupied orbitals of the graphene into three orbitals with distinct energy levels. White emission is achieved by combining the quantum dots with other emissive materials in a multilayer light-emitting diode.     

Predicting the morphology of nanostructured composites

The mixing of microphase-separating diblock copolymers and nanoparticles can lead to the self-assembly of organic/inorganic hybrid materials that are spatially organized on the nanometer length scale. There is a considerable challenge in modeling such systems since the appropriate theories must capture not only the formation of the diblock mesophases but also the copolymer–particle and particle–particle interactions, which can affect the ultimate structure of the material. Recently, a theoretical approach has been developed to describe the behavior of diblock/particle mixtures and predict the equilibrium morphology of the resulting composites. The approach, which combines self-consistent field and density functional theories, can facilitate the design of hybrid materials with the desired morphology for novel opto-electronic devices, separation membranes and catalysts.     

燃料电池用质子电解质的研究进展

目前,作为燃料电池的重要部件的质子电解质主要分为有机、有机一无机复合、无机三类.有机质子电解质接近商业化程度,但其价格昂贵,中温导电性差;复合质子电解质是以前者为基础掺杂增湿组分,使燃料电池性能有一定程度的增强;提高工作温度是解决燃料电池中催化荆CO中毒和提高燃料转化效率的有效办法,因此能在中高温环境中工作的无机质子导电材料已成为研究热点之一.     

Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice

Materials science evolves to a state where the composition and structure of a crystal can be controlled almost at will. Given that a composition meets basic requirements of stoichiometry, steric demands, and charge neutrality, researchers are now able to investigate a wide range of compounds theoretically and, under various experimental conditions, select the constituting fragments of a crystal. One intriguing playground for such materials design is the perovskite structure. While a game of mixing and matching ions has been played successfully for about 150 years within the limits of inorganic compounds, the recent advances in organic–inorganic hybrid perovskite photovoltaics have triggered the inclusion of organic ions. Organic ions can be incorporated on all sites of the perovskite structure, leading to hybrid (double, triple, etc.) perovskites and inverse (hybrid) perovskites. Examples for each of these cases are known, even with all three sites occupied by organic molecules. While this change from monatomic ions to molecular species is accompanied with increased complexity, it shows that concepts from traditional inorganic perovskites are transferable to the novel hybrid materials. The increased compositional space holds promising new possibilities and applications for the universe of perovskite materials.