新型金属-有机骨架配位聚合物（MOF）的研究龈

金属有机骨架配位聚合物结构多样,性质独特,具有广泛的应用前景,它已成为近几年来一个热门的研究领域,如今它因H2存储方面的潜力受到广泛关注。本文简要介绍该类配位聚合物作为一种新型的多孔材料,在结构和性能方面的研究进展。     

基于Co(Ⅱ)配合物前驱体的微纳米Co_3O_4功能材料的研究进展

金属有机骨架化合物(MOFs)是由有机配体和金属节点通过自组装形成的一类具有周期性结构和较大比表面积的材料。目前,选择MOFs材料作为前驱体,经高温焙烧合成纳米金属氧化物或纳米复合金属氧化物材料是一大研究热点。综述了近年来以Co基配位聚合物为前驱体制备纳米Co_3O_4或Co_3O_4/碳纳米复合材料的方法,以及Co_3O_4纳米材料在锂离子电池负极材料、超级电容器、电催化析氧反应、气敏材料及催化剂材料等研究领域的应用,并对其今后的发展进行了展望。     

配位聚合物的研究进展

综述了近年来比较热门的研究领域——配位聚合物,它是由过渡金属和有机配体自组装而形成的,具有独特的空间几何构型,在非线性光学材料、磁性材料、超导材料,微孔材料及非对称催化等诸多方面都有广阔的应用前景。本文就不同配体的配位聚合物进行了分类研究。     

Design and synthesis of porous polymeric materials and their applications in gas capture and storage: a review

The design and synthesis of porous organic materials that have increasing physical and chemical characteristics have been discussed. For example, a variety of porous organic polymers, metal–organic frameworks, conjugated microporous polymers, and polymers of intrinsic microporosity have been designed and synthesized using simple and efficient procedures. Such materials have unique gas adsorption properties and can be used in gases separation and storage. In addition, they have high surface area, porosity, and selectivity towards carbon dioxide compared to other gases such as nitrogen and methane.     

含磷多孔有机聚合物的合成及其在多相催化中的应用

含磷多孔有机聚合物不仅具有发达的孔隙和表面结构,还具有很强的可调变性和可修饰性,在多相催化中有着广泛的应用前景。目前还没有概述含磷多孔有机聚合物的制备及其在多相催化中应用的综述,本文对该领域近十年来的研究进展进行了归纳和梳理。指出含磷多孔有机聚合物的合成方法发展十分迅速,包括偶联缩聚、锂盐参与的缩聚、Friedel-Crafts缩聚、溶剂热烯烃聚合、Scholl缩聚、酚醛聚合、醛胺缩合、聚吡喃盐的磷代以及多段式聚合等。基于其骨架中含有大量膦配体,含磷多孔有机聚合物能负载一系列金属化合物制成负载型金属纳米颗粒催化剂,甚至单原子或单位点金属催化剂。表明聚合物基催化剂中,膦配体不仅能诱导金属在聚合物中均匀分布,并且在调控金属的表面电子性质和位阻性质等方面发挥重要作用,进而对催化剂的活性和选择性产生影响。     

Review on Polymer Materials for Solid Desiccant Cooling System

As an alternative form of vapor compression air conditioning devices, solid desiccant cooling (SDC) techniques have increasingly been explored recently. The overall performances of SDC primarily rely on the capability of dehumidification and regeneration of desiccant. A desiccant with a great uptake capability and excellent regeneration potential is preferred in an SDC system. Although traditional desiccants like silica gels and zeolites are able to absorb moisture at moderate levels, hygroscopic polymers show a superior ability in moisture sorption and desorption. Significant research has been conducted to investigate the hygroscopic polymers in SDC for household and industrial applications. Here, first, an introduction to SDC systems is presented, and then hygroscopic polymers from natural and synthetic origins are discussed. Synthetic polymers discussed are metal–organic frameworks (MOFs), covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), amorphous porous organic polymers (POPs), polyelectrolytes, and polymer-based composites. Their dehumidification behaviors in SDC systems, primarily desiccant-coated heat exchanger (DCHE) systems, are compared and summarized. Binders employed in SDC systems are also summarized, as a proper binder enhances the overall performance of the desiccant system. It can be anticipated that hygroscopic polymers and binder materials would witness extensive applications in the future.     

研磨法制备金属有机框架材料的新进展

金属有机框架材料是由金属离子/团簇和具有一定刚性结构的有机配体通过配位键连接而成的多孔晶体材料,具有多孔、比表面积大、结构多样、表面易修饰等特点,在能源、化工、医药领域具有广泛的应用。机械化学合成法是指通过机械能诱导化学反应的方法,由于其绿色环保、耗时短、效率高、应用范围广、副反应少的特点近年来受到广泛关注,在制备金属有机框架材料方面同样表现出显著的优势。研磨法是机械化学合成法中重要的一种。为了解生物金属骨架材料的机械化学法合成概况及最新进展,本文介绍了研磨法制备金属有机框架材料的经典案例,尤其着重介绍了应用于医药领域的金属有机框架材料的合成,研究进展表明研磨法是一种绿色高效的合成方法,为金属有机框架材料在医药领域的广泛应用提供了可能,具有良好的发展前景。     

氨气吸附材料的研究进展

氨是一种典型的有毒有害气态碱性污染物,也是PM2.5二次颗粒物的主要成因之一,大量含氨尾气排放不仅严重影响人类健康和生活环境,还会造成氨资源浪费。本工作综述了近年来多孔材料用于氨气吸附分离的研究现状和进展,重点论述了沸石、硅胶、活性炭、氧化石墨烯、多孔有机聚合物、共价有机骨架和金属?有机骨架材料改性前后对氨气的吸附性能,总结了吸附材料的改性方法,分析了该领域发展面临的主要问题,对未来的研究方向提出了建议。     

Progress of superhydrophobic porous materials

Porous materials such as metal organic framework materials (MOFs), covalent organic framework materials (COFs), organic porous polymers (POPs), etc., have been used widely used in the fields of separation, catalysis, gas storage and drug release due to their diversity, designability, controllability and functionalization of pores. Despite these promising applications, some of the porous materials suffer from moisture-sensitivity and instability in aqueous media due to their inherent structural features. To overcome this problem, endowing them with hydrophobicity is an effective strategy. However, designing superhydrophobic porous materials has certain challenges. In this work, the progress of MOFs, COFs and POPs with (super-)hydrophobic property is introduced. Issues related to their design strategy, structures, and practical applications such as catalysis, oil/water separation and gas storage and separation were analyzed. Additionally, the current problems and the future research directions of the hydrophobic porous materials were discussed.     

超疏水多孔材料的研究进展

多孔材料如金属有机框架材料（MOFs）、共价有机框架材料（COFs）、有机多孔聚合物（POPs）等由于构筑单元的多样性、可设计性,孔道的可调控性和功能化,已经被广泛用于分离、催化、气体储存以及药物释放等领域。尽管如此,这些多孔材料固有的结构特征让它们普遍对水气非常敏感,最严重时多孔结构在水溶液环境下会坍塌。为解决此类问题,制备疏水的多孔材料是一个非常好的策略。然而,设计超疏水多孔材料具有一定的挑战。介绍了具有（超）疏水性能的MOFs、COFs和POPs的发展现状,对超疏水多孔材料合成思路和结构特点进行了分析,对这类材料在催化、油水分离、气体吸附和分离等方面的应用进行了总结,并进一步探讨了此类材料存在的问题和发展方向。     

金属有机框架材料的绿色合成

金属有机框架化合物（Metal-organic frameworks,简称MOFs）是由金属离子（或簇）与有机配体配位并经由自组装而形成的一类多孔材料^[1]。MOFs具有极其发达的孔道结构,比表面积和孔容远超其他多孔材料。有机/无机杂化这一特点也赋予了MOFs其他材料（例如沸石、活性炭等）所不具备的无限结构功能可调性^[2]。此外,MOFs具有移除客体分子而主体框架完好保持的持久孔道或孔穴,这使得MOFs具有超乎寻常的化学及物理稳定性。正是基于以上这些特点,MOFs在许多领域有着丰富的应用^[3-4],例如催化^[5]、H₂储存^[6]、CO₂捕集^[7]、药物运输^[8]、污染物吸附^[9]、生物医学成像^[10]等方面。MOFs的商业化探索成为了目前的热点。MOFs的很多应用都与可持续发展及“绿色材料”有关,但MOFs本身的合成过程也需要考虑可持续性和环境影响。金属有机化学所面临的环境挑战是独特的,因为它将金属离子、有机配体的危害联系在一起,且合成过程大多需要大量能耗。主要介绍了金属有机框架材料的绿色可持续合成,主要分为4个方面：1）使用更安全或生物相容性的配体;2）使用更绿色、低成本的金属源;3）绿色溶剂的开发;4）无溶剂合成法。     

金属有机骨架材料多功能阻燃聚合物应用研究进展

简要介绍了具有高孔隙率、催化吸附等特性的金属有机骨架(MOFs)材料的分类及合成方法,分别从改性以及未改性MOFs材料在聚合物中的阻燃应用及阻燃机理来阐述了近年来MOFs材料在聚合物材料阻燃方面的研究现状.最后,对其MOFs材料的应用前景进行了总结与展望.     

氨气深度脱除材料与技术研究进展

氨气（NH₃）作为一种危害性碱性有毒气体,不仅危害环境,而且会对人体造成不可逆伤害。在电子信息、能源等行业,极微量的NH₃即可影响产品品质、降低过程性能。因此,NH₃的深度脱除在工业上具有重要的意义。本文综述了近年来NH₃深度脱除的工艺现状,分析了NH₃脱除材料如离子液体、低共熔溶剂、改性活性炭、分子筛、改性氧化铝、金属盐类、金属有机框架材料、多孔有机聚合物、共价有机骨架材料、氧化石墨烯、普鲁士蓝类似物对NH₃的分离性能。总结了深度脱除NH₃的工艺特点和脱氨材料的性能,浅析了该领域发展面临的问题,并对未来的发展方向提出了建议。     

Applications of Metal-Organic Frameworks as Drug Delivery Systems

In the last decade, metal organic frameworks (MOFs) have shown great prospective as new drug delivery systems (DDSs) due to their unique properties: these materials exhibit fascinating architectures, surfaces, composition, and a rich chemistry of these compounds. The DSSs allow the release of the active pharmaceutical ingredient to accomplish a desired therapeutic response. Over the past few decades, there has been exponential growth of many new classes of coordination polymers, and MOFs have gained popularity over other identified systems due to their higher biocompatibility and versatile loading capabilities. This review presents and assesses the most recent research, findings, and challenges associated with the use of MOFs as DDSs. Among the most commonly used MOFs for investigated-purpose MOFs, coordination polymers and metal complexes based on synthetic and natural polymers, are well known. Specific attention is given to the stimuli- and multistimuli-responsive MOFs-based DDSs. Of great interest in the COVID-19 pandemic is the use of MOFs for combination therapy and multimodal systems.     

Nanofabrication with metallopolymers ‐ recent developments and future perspectives

Synthetic polymers containing metals and metal centers have experienced rapid growth in the last two decades. Metal‐containing polymers have an unprecedented role to play in modern high‐tech applications including nanomanufacturing, sensing, separation and catalysis. Advancement in synthetic strategies for macromolecules has enabled the synthesis of novel, exotic and use‐inspired metallopolymers. Using state‐of‐the‐art design strategies, it is now possible to perform targeted synthesis of macromolecules with varied complexity that contain a range of metal centers either in the backbone or in the side chains of the organic moiety. The presence of an inorganic element (metals and metal centers) in organic moieties has led to a number of new physicochemical properties while implementing novel functionality to the polymer matrix. This review covers nanotechnology influenced by distinctive features of metal‐containing macromolecular systems, particularly in developing flexible, functional materials. © 2013 Society of Chemical Industry     

光子功能金属-有机框架材料研究进展

金属-有机框架材料是一种由金属离子或金属簇与有机桥联配体通过配位作用组装形成的新型无机-有机复合多孔材料.无机、有机组分在分子水平的复合使得框架材料能够兼具无机和有机基元各自的特点和性能并产生协同作用,有序微孔则为组装客体分子实现光子学性能的调控甚至新光子功能的出现提供了可能.金属-有机框架材料在发光和非线性光学等光子...     

Stereospecific polymerization of olefins with supported Ziegler − Natta catalysts

The discovery of Ziegler ? Natta catalysts has been one of the greatest developments in technology for the synthesis of stereoregular polymers in both academy and industry since the 1950s. In particular, the development of the fourth generation Ziegler ? Natta catalyst with MgCl₂ as support brings a revolutionary improvement to the properties of manufactured polyolefins and stimulates people to explore the stereospecific polymerization of α‐olefin and diene monomers, which supplies the power to synthesize a new type of polyolefin materials. Although research on single‐site catalysts has attracted a lot of attention in recent years, the ‘old’ and conventional Ziegler ? Natta catalysts are still being developed vigorously due to their unique industrial advantages such as low cost, high catalytic efficiency and high stereospecificity. In this mini‐review, we mainly summarize the development of the conventional supported Ziegler ? Natta catalyst system and the stereoregular polyolefins synthesized with supported Ziegler ? Natta catalysts. © 2013 Society of Chemical Industry     

Tuning the topology and functionality of metal-organic frameworks by ligand design

Metal-organic frameworks (MOFs)-highly crystalline hybrid materials that combine metal ions with rigid organic ligands-have emerged as an important class of porous materials. The organic ligands add flexibility and diversity to the chemical structures and functions of these materials. In this Account, we summarize our laboratory's experience in tuning the topology and functionality of MOFs by ligand design. These investigations have led to new materials with interesting properties. By using a ligand that can adopt different symmetry conformations through free internal bond rotation, we have obtained two MOFs that are supramolecular stereoisomers of each other at different reaction temperatures. In another case, where the dimerized ligands function as a D(3)-Piedfort unit spacer, we achieve chiral (10,3)-a networks. In the design of MOF-based materials for hydrogen and methane storage, we focused on increasing the gas affinity of frameworks by using ligands with different geometries to control the pore size and effectively introduce unsaturated metal centers (UMCs) into the framework. Framework interpenetration in PCN-6 (PCN stands for porous coordination network) can lead to higher hydrogen uptake. Because of the proper alignment of the UMCs, PCN-12 holds the record for uptake of hydrogen at 77 K/760 Torr. In the case of methane storage, PCN-14 with anthracene-derived ligand achieves breakthrough storage capacity, at a level 28% higher than the U.S. Department of Energy target. Selective gas adsorption requires a pore size comparable to that of the target gas molecules; therefore, we use bulky ligands and network interpenetration to reduce the pore size. In addition, with the help of an amphiphilic ligand, we were able to use temperature to continuously change pore size in a 2D layer MOF. Adding charge to an organic ligand can also stabilize frameworks. By ionizing the amine group within mesoMOF-1, the resulting electronic repulsion keeps the network from collapsing, giving rise to the first case of mesoporous MOF that demonstrates the type IV isotherm. We use dendritic hexacarboxylate ligands to synthesize an isoreticular series of MOFs with (3,24)-connected network topology. The cuboctahedral cages serve as building blocks that narrow the opening of the mesocavities into microwindows and stabilize these MOFs. The resulting materials have exceptionally high surface areas and hydrogen uptake capacities. Despite the many achievements in MOF development, there is still ample opportunity for further exploration. We will be continuing our efforts and look forward to contributing to this blossoming field in the next decade.     

金属有机骨架材料在后合成修饰中的应用

金属有机骨架材料（MOFs）作为一类配位聚合物,具有孔洞结构、高比表面和独特的化学调变性。后合成修饰（PSM）能为MOFs的骨架引进新的官能团,改变MOFs的孔道环境,调变MOFs骨架的理化性质,有利于MOFs在更专属、更复杂领域的应用。本文对金属有机骨架材料（MOFs）在合成修饰中的应用进行了综述。     

Hydrogen adsorption and storage on porous materials

The development of safe and efficient methods of hydrogen storage is a prerequisite for the use of hydrogen with fuel cells for transport applications. In this paper, results available for adsorption of hydrogen on porous materials, ranging from activated carbons to metal organic framework materials, are discussed. The results indicate that up to 5 and 7.5 wt% of hydrogen can be stored on porous carbon and metal organic framework materials, respectively, at 77 K. The amounts of hydrogen adsorbed on porous materials at ambient temperatures and high pressures are much lower (0.5 wt%). The strong temperature dependence of hydrogen physisorption on porous materials is a limitation in the application of this method for hydrogen storage in addition to storage capacity requirements.