Preface to Special Column on New Porous Catalytic Materials

Over the last 15-20 years a wide range of new porous catalytic materials has been discovered in the wake of major developments in mesostructured materials and hybrid porous solids such as metal organic frameworks (MOFs).These two developments have both enormous potential to produce catalyst supports and solids.It may be argued that most existing industrial catalysts may be revisited for improvement taking advantage of the novel materials.In both cases new techniques allow controlling not only specific surface area and pore volume but even more importantly pore size distribution and therefore the diffusional properties of reactants and products.     

Metal-Organic Frameworks-Based Fluorescent Nanocomposites for Bioimaging in Living Cells and in vivo

Metal-organic frameworks(MOFs)as a class of porous functional materials have attracted more and more attention for biomedical applications.To date,MOFs have been developed for bioimaging based on a series of advantages such as the large surface areas,high porosity,fluorescence functionalities and good biocompatibility.It is worth noting that organic or inorganic fluorescent materials such as fluorescent dyes,quantum dots,metal nanoclusters and nanosheets can combine MOFs or be encapsulated in MOFs to form fluorescent nanocomposites for excellent imaging function.Importantly,excellent imaging capabilities are of great significance in living cells and in vivo for detection,diagnosis and cancer therapy.In this review,we focus on the recent research of the bioimaging in living cells and in vivo based on various MOF-based nanocomposites and their potential biological clinical applications.     

Recent advance in synthesis and application of heteroatom zeolites

Incorporation of heteroatoms into the framewo rk of zeolites has become a significant strategy to improve their performance in catalysis and adsorption,because the obtained heteroatom zeolites exhibit quite different properties from the conventional aluminosilicate zeolites in aspects of surface acidity,pore structures,particle size and so on.In this review,the progress on the heteroatom zeolites including their synthesis and application is highlighted.First,the recent advance on the design and synthesis of different heteroatom zeolites is summarized.Special emphasis is placed on the introduction and comparison of three typical methods,including the direct synthesis,post synthesis and improved direct synthesis,for the traditional heteroatom zeolites(such as TS-1,Sn-MFI,Sn-β) and newly-reported heteroatom zeolites(such as W-MFI,Mo-MFI).According to their intrinsic characteristics,the application of heteroatom zeolites in diverse fields,such as production of fine chemicals,air pollution control and biomass conversion is then discussed.Finally,the challenges and perspective on the future development of heteroatom zeolites in low-cost preparation and practical application are proposed.     

Promise and challenge of vanadium-based cathodes for aqueous zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs)have got wide attention with the increasing demands for energy resource recently.It has a number of merits compared with lithium-ion batteries,such as enhanced safety,low cost and environmental friendliness.Vanadium-based materials have been developed to serve as the cathodes of ZIBs for many years.But there are also some challenges to construct high performance ZIBs in the future.Herein,we reviewed the research progress of vanadium-based cathodes and discussed the energy storage mechanisms in ZIBs.In addition,we summarized the major challenges faced by vanadium-based cathodes and the corresponding ways to improve electrochemical performance of ZIBs.Finally,some excellent vanadium-based cathodes are summarized to pave the way for future research in ZIBs.     

Metal-organic frameworks and their derivatives for Li-air batteries

Metal-organic frameworks(MOFs)are a class of outstanding materials in Li-air batteries because of their high surface areas,tailorable pore sizes and diverse catalytic centers.However,MOF-based batteries are facing challenges such as poor electronic conductivity and inferior long-cycle stability that limit their further development.This review first summarizes the progress of pristine MOFs and MOF-derived materials in Li-air batteries in the past 5 years,then provides a perspective for subsequent development of MOFs and their derivatives in this emerging field.     

Designing ABC-6 family small pore zeolites by epitaxial growth approach

Aluminosilicate small pore zeolites belonging to ABC-6 family play crucially important roles in the high methanol conversion with the high selectivity of light olefins, gas separation and storage, and selective catalytic reduction of NO_x. In this work, we report a general method, called the epitaxial growth approach, for designing ABC-6 family small pore zeolites. It is mainly realized through the epitaxial growth on the nonporous SOD-type zeolite in the presence of inorganic cations(...     

Nanoscale 3D ordered polymer networks

Structures having nanoscale 3 D geometries are valuable as multifunctional materials, where multi-continuous microphases can synergistically influence mechanical, optical, transport and other properties. Such very high interface surface to volume ratio structures occur in a variety of materials including natural materials such as butter fly wings and sea urchin exoskeletons and in synthetic self-assembled structures such as surfactant/water systems and block polymers. Quantitative morphological characterization of such complex geometric structures is quite challenging. Unit cell sizes range from 10–300 nm with corresponding feature sizes on the 2–50 nm scale. Since these nanoscale network structures are bicontinuous, when one constituent is removed, the structure is still self supporting. Removal of one component produces a nanoporous material that may be in-filled with another component, or the surfaces of the nanopores can be coated with ultra-thin layers by atomic layer deposition to offer multifunctional capabilities. Due to the ability to individually tailor the properties of the network(s) and matrix,for example, to create strong dielectric or impedance contrast, such spatially periodic structures are excellent for the interference of waves(electromagnetic for photonic applications and acoustic for phononic applications) that can lead to bandgaps and hence the control of wave propagation in the material. This mini-review will focus on networks formed by bottom up self assembly of block polymers. In addition to structural issues, we emphasize the special physical properties related to bi-or tri-continuous networks.     

Recent Progress in Shape Memory Polymers for Biomedical Applications

Shape memory polymers (SMPs) as one type of the most important smart materials have attracted increasing attention due to their promising application in the field of biomedicine,textiles,aerospace et al.Following a brief intoduction of the conception and classification of SMPs,this review is focused on the progress of shape memory polymers for biomedical applications.The progress includes the early researches based on thermo-induced SMPs,the improvement of the stimulus,the development of shape recovery ways and the expansion of the applications in biomedical field.In addition,future perspectives of SMPs in the field of biomedicine are also discussed.     

The “bottom-up” synthesis and applications of persistent luminescence nanoparticles

正Persistent luminescence refers to the phenomenon whereby luminescence remains after excitation ceases.In the past few decades,various kinds of persistent luminescent materials have been developed and widely employed in numerous applications,such as security signs,medical diagnostics and photocatalysis.Persistent luminescent materials offer distinctive advantages for biomedical applications,especially for bioimaging,as they can efficiently avoid autofluorescence and tissue-scattered light interference[1].Since     

Recent Advances on Metal-Organic Frameworks in the Conversion of Carbon Dioxide

With the development of modern industry,global warming is becoming a challenging issue due to the emissions of large quantities of greenhouse gases,mainly carbon dioxide(CO₂).The conversion of CO₂to useful compounds is considered as an effective and economic way to solve such a climate problem.Metal-organic frameworks(MOFs)are an emerging class of porous crystalline materials that have shown great potential in the conversion of CO₂.The advantages of MOFs in CO 2 conversion lie in their high surface areas,adjustable pore size,and high porosity.More importantly,desirable functional sites can be easily designed and precisely installed to the pore wall of target MOFs by pre-assembly and/or post-synthetic modification(PSM)ways.This review summarizes the recent advances in constructing MOF catalysts for the application in CO₂conversion.We believe that the design and synthesis of MOF catalysts for CO₂conversion can be a promising way to solve the“greenhouse effect”.     

金属-有机骨架材料用于废水处理

废水中的各种有害物质常常具有生物毒性或致癌性,因此如何高效、节能地处理水体污染是一个亟待解决的重要问题。金属-有机骨架材料(metal-organic frameworks, MOFs)是一种新型纳米多孔材料,具有种类多样性、结构可设计性与可调控性、高比表面积及良好的热稳定性等优点,已成为当前化学、材料学科的一个研究热点, 在多个领域显示出潜在的应用前景,尤其是在分离方面。与气相分离相比,MOFs用于液相分离的研究较少。本文综述了近年来MOFs用于含有染料、药物、醇、芳香族化合物、重金属离子及其他离子的废水处理的研究进展,重点剖析了MOFs的孔结构、骨架电荷及功能性对分离效果的影响,并结合本课题组的研究工作,对这种新型多功能材料在水处理方面的前景和今后的研究重点作了展望。     

金属有机骨架材料在吸附分离大气污染物中的应用

大气污染问题是关系人民生命健康和经济社会和谐发展的重大问题.因此需要开发高效的吸附材料用于大气污染物的吸附和分离.金属有机骨架材料(MOFs)是一类新型的多孔材料,该材料具有结构多样、孔结构有序、大比表面积和高孔隙率等结构特点.MOFs通过调节有机配体的长度和官能团调节孔径和孔道尺寸,并进行功能化修饰在孔道中引入功能性...     

Engineering Metal–Organic Framework Catalysts for C−C and C−X Coupling Reactions: Advances in Reticular Approaches from 2014–2018

Metal–organic frameworks (MOFs) are a class of crystalline porous materials that have been actively used for several industrial and synthetic applications. MOFs are spatially and geometrically extrapolated coordination polymers with intriguing properties such as tunable porosity and dimensionality. In terms of their catalytic efficiency, MOFs combine the easy recoverability of heterogeneous catalysts with the increased selectivity of biological catalysts. It is therefore not surprising that a lot of work on optimizing MOF catalysts for organic transformations has been carried out over the past decade. In this review, recent developments in MOF catalysis are summarized, with special attention being paid to C−C, C−N, and C−O coupling reactions. The influence of pore size, pore environment, and load on catalytic activity is described. Post-synthetic stabilization techniques and host–guest interactions in caged MOF scaffolds are detailed. Mechanistic aspects pertaining to the use of MOFs in asymmetric heterogeneous catalysis are highlighted and categorized.     

Mesoporous metal-organic framework materials

Metal-organic frameworks (MOFs) have emerged as a new type of porous materials for diverse applications. Most open MOFs reported to date are microporous (pore sizes <2 nm), and only a small fraction of MOFs with ordered mesoscale domains (2-50 nm) is reported. This tutorial review covers recent advances in the field of mesoporous MOFs (mesoMOFs), including their design and synthesis, porosity activation and surface modification, and potential applications in storage and separation, catalysis, drug delivery and imaging. Their specificities are dependent on the pore shape, size, and chemical environments of the cages or channels. The relationship between the structures and functions is discussed. The future outlook for the field is discussed in the context of current challenges in applications of mesoporous materials.     

金属有机框架膜的制备及应用

金属有机框架化合物是一类新颖的纳米孔结晶材料,其由金属离子或簇以强的配位键形式连接多种多样的有机配体构成．金属有机框架化合物的均一孔径、高比表面积和吸附亲和力等独特的结构特点使其在组装成具有优异性能的膜方面具有很强的吸引力．金属有机框架膜在基础理论和实际应用方面显示了巨大的潜力．本文主要介绍近年来关于金属有机框架膜的制备及其在分离、化学传感、催化和电化学中的应用等研究,同时指出了目前需要克服的问题．     

Site characteristics in metal organic frameworks for gas adsorption

Metal organic frameworks (MOFs) are a new class of nanoporous materials that have many potential advantages over traditional nanoporous materials for several chemical technologies including gas adsorption, catalysis, membrane-based gas separation, sensing, and biomedical devices. Knowledge on the interaction of guest molecules with the MOF surface is required to design and develop these MOF-based processes. In this review, we examine the importance of identification of gas adsorption sites in MOFs using the current state-of-the-art in experiments and computational modeling. This review provides guidelines to design new MOFs with useful surface properties that exhibit desired performances, such as high gas storage capacity, and high gas selectivity.     

分子筛限域金属纳米粒子及其氧化还原反应应用的研究进展

沸石分子筛是一类孔隙均匀、结晶度高、结构多样、比表面积大的材料,在催化、分离、吸附等方面得到了广泛的应用。沸石分子筛已被证明是金属纳米粒子(MNPs)的理想载体。金属纳米粒子@沸石分子筛催化剂不仅表现出优异的催化活性,而且具有较高的稳定性和择形催化性。此外,限域的金属纳米粒子与具有活性位点的纳米孔骨架的协同作用可以进一步提高复合催化剂的催化活性。金属纳米粒子@沸石分子筛催化剂由于具有较高的活性、择形性和热稳定性等优点,在工业相关应用中引起了人们的极大关注。本文综述了金属纳米粒子@沸石分子筛催化剂的研究进展,重点介绍了多种合成方法以及其在氢化和氧化反应中的应用进展。指出了金属纳米粒子@沸石分子筛催化剂领域存在的问题和挑战并对其未来发展进行展望。     

Swelling, functionalization, and structural changes of the nanoporous layered silicates AMH-3 and MCM-22

Nanoporous layered silicate materials contain 2D-planar sheets of nanoscopic thickness and ordered porous structure. In comparison to porous 3D-framework materials such as zeolites, they have advantages such as significantly increased surface area and decreased diffusion limitations because the layers can potentially be exfoliated or intercalated into polymers to form nanocomposite materials. These properties are particularly interesting for applications as materials for enhancing molecular selectivity and throughput in composite membranes. In this report, the swelling and surface modification chemistry of two attractive nanoporous layered silicate materials, AMH-3 and MCM-22, were studied. We first describe a method, using long-chain diamines instead of monoamines, for swelling of AMH-3 while preserving its pore structure to a greater extent during the swelling process. Then, we describe a stepwise functionalization method for functionalizing the layer surfaces of AMH-3 and MCM-22 via silane condensation reactions. The covalently attached hydrocarbon chain molecules increased the hydrophobicity of AMH-3 and MCM-22 layer surfaces and therefore allow the possibility of effectively dispersing these materials in polymer matrices for thin film/membrane applications.     

Synthesis of symmetrical alkyl-aromatics by use of shape selective catalysts

The concept of shape selectivity is available to produce symmetrical dinuclear aromatic hydrocarbons such as 2,6-dialkylnaphthalene and 4,4′-dialkylbiphenyl, which are the raw materials for liquid crystals and polyester with superior properties, respectively. The ZSM-5 catalyst exhibits high activity and selectivity for the formation of p-xylene in the disproportionation and alkylation of toluene. The catalytic activity of ZSM-5 for the conversion of naphthalene derivatives is markedly low due to its small pore size, although symmetrical dinuclear aromatic hydrocarbons are selectively formed. The high catalytic activity is obtained with twelve-membered ring zeolites. Among these zeolites, mordenite is the most selective catalyst to produce symmetrical dinuclear aromatic hydrocarbons. The precise controls of the size of pore opening and the acidic property are required to enhance the selectivity for symmetrical dinuclear aromatic hydrocarbons. The non-zeolitic molecular sieves also present a great opportunity in high selective synthesis of these compounds.     

Recent Advances on Confining Noble Metal Nanoparticles Inside Metal-Organic Frameworks for Hydrogenation Reactions

Hydrogenation reaction is one of the pillars of the chemical industry for the synthesis of drugs and fine chemicals. To achieve high catalytic performance, it is still highly desirable for constructing novel supported metal catalysts. Different from conventional supports like metal oxides, zeolites and carbon materials, metal-organic frameworks(MOFs) as the emerging porous materials have Hexhibited great potential to host metal nanoparticles (NPs) for achieving hydrogenation reactions with high catalytic efficiency, due to their unique porous structures. Recently, many progresses have been made, and thus, it is necessary to summarize the recent progresses on confining metal NPs inside MOFs for hydrogenation reactions. In this review, we first introduced the general synthesis methods for confining noble metal NPs inside MOFs. Then, the applications of noble metal NPs/MOFs catalysts in hydrogenation reactions were summarized, and the synergistic catalytic performances among noble metal NPs, metal nodes, functional groups, and pore channels in MOFs were illustrated. Subsequently, the hydrogen spillover effect involved in the hydrogenation reactions was discussed. Finally, we provide an outlook on the future research directions and challenges of confining noble metal NPs inside MOFs for hydrogenation reactions.