以MgO为模板剂制备纳米中孔炭及其应用研究进展

无需任何稳定和活化过程,采用MgO为模板剂,选择不同的碳前驱体可制备高比表面积且含有大量中孔的活性炭.综述了具体制备方法、制备条件对孔结构的影响、纳米孔结构形成机理、该方法的优点以及该法所得纳米中孔活性炭的应用前景.通过选择不同的MgO前驱体可调节活性炭中孔大小;而中孔和微孔的相对体积则由碳前驱体控制.采用该法制备的中孔炭作为电容器、吸附材料等在能源、资源和环境方面的应用前景相当广阔.     

不同模板剂对介孔氧化铝孔径调节作用

以醇铝为原料,利用三种不同类型的模板剂对氧化铝的孔径进行调节,对各种模板剂的作用机理进行了初步探讨.研究结果表明：不同模板剂获得的介孔氧化铝的孔道结构基本一致,均为蠕虫状结构,模板剂的不同对介孔氧化铝孔径的影响较大,未加模板剂直接由溶胶-凝胶法获得的介孔氧化铝孔径分布较窄,孔径偏小;加入离子型模板剂能够形成孔径分布窄、孔径增大的介孔材料;加入非离子型模板剂则形成孔径更大,但孔径分布较宽的介孔氧化铝.     

高分子聚合物模板剂制备介孔材料的研究

高聚物模板剂在介孔材料的合成中起着重要的作用,选择不同的高聚物模板剂可以合成出具有不同形态结构的介孔材料。对介孔材料合成中使用的高聚物模板剂如单一高聚物模板剂、复合高聚物模板剂和天然高聚物模板剂等,进行了综述。     

金属有机骨架材料合成方法对氮氧化物吸附性能的影响

金属有机骨架材料(Metal-organic frameworks,MOFs)因具有高的比表面积和孔隙率,使得其拥有良好的气体吸附性能.与传统的NOx吸附材料相比,MOFs材料拥有超高的比表面积和孔隙率,结构丰富多样且具有周期性,良好的热稳定性和化学稳定性.国内外学者采用不同的合成方法合成MOFs材料,以达到对NOx高效吸附的目的.MOFs材料的合成方法主要有水热法、溶剂热法、超声波合成法和微波合成法.水热法操作步骤简单,合成的晶体质量高,但是晶粒较大,孔体积小;溶剂热法和水热法原理相同,通过加入不同官能团的有机溶剂,合成的材料结构更为丰富,比表面积和孔容更大,对NOx的吸附效果比水热法好,也是使用最广泛的方法;超声波合成法合成的MOFs材料粒径较小且尺寸均一,比表面积和孔容较大,对NOx的吸附效果好,但是成本较高;微波合成法可加快反应速率,形成更小的晶粒,比表面积和孔容较大,对NOx的吸附量很高,但是同样也具有经济成本高的劣势.为此,本文对MOFs材料的合成方法、改性技术进行了总结,同时分析了不同方法合成的MOFs对氮氧化吸附效果的影响,并对MOFs材料吸附氮氧化物的发展趋势作了展望.     

基于低聚酰亚胺含氮介孔碳材料的制备

以低聚酰亚胺为氮源前驱体、交联酚醛树脂为碳源、嵌段共聚物为软模板剂,通过相分离自组装、交联和高温锻烧处理制备了新型高规整含氮介孔碳材料,并用FT-IR、SEM、TEM、热重分析和小角X光散射等测试方法表征介孔碳材料的组成与结构.结果表明,处理温度达350℃时嵌段共聚物模板可被成功移除,进而形成多孔结构;温度达600℃时体系完全碳化,可得到高规整的多孔含氮碳材料.通过调节体系中氮源、碳源及模板剂的相对比例可实现形貌由立方结构向柱状和层状结构的过渡,进而实现对含氮介孔材料形貌的有效调控.     

金属有机骨架在水环境治理领域的应用

金属有机骨架(MOFs)由金属节点与有机配体通过配位键连接而成的多孔网络框架材料,其具有高比表面积和孔隙率以及丰富可调的孔结构,使其成为广泛关注的研究热点之一。对近几年来MOFs在水环境治理领域,特别是对重金属离子和有机污染物治理领域的研究进展进行了综述;讨论了MOFs通过构件分子和孔结构的修饰与调控对水中污染物的吸附机理;指出作为吸附剂MOFs最大的优越性在于,可根据目标污染物分子、离子的特点,在MOFs中引入不饱和金属位点和各种官能团和对骨架结构、孔隙大小和孔表面物理化学特性进行调控,以达到增大吸附选择性、增加吸附容量、提高吸附速率的目的,在吸附法去除重金属离子和有机污染物治理领域的有很大的潜力。同时,在合成MOFs时采用环境友好的构建分子,避免二次污染,并逐步降低成本。     

聚合物基MOFs复合材料的制备及应用

金属有机骨架化合物(MOFs,配位聚合物)主要是由金属离子与有机配体通过自组装作用而形成的一种有机无机多孔配合物,它具有结构可调、孔隙率高以及比表面积大等特点,在生物医药、传感、气体分离膜等方面有着广泛的应用,但单一的MOFs材料也有一定的缺点,如稳定性差、机械强度低等。为了改善其缺点,一些研究者将MOFs材料与无机物、有机物复合,在改善MOFs材料缺陷的同时扩宽它的应用范围,本文重点阐述了MOFs材料与聚合物的复合研究进展。本文根据MOFs材料的命名、组分单元和合成方法的不同将MOFs分为以下几类,如网状金属有机骨架材料(IRMOFs)、类沸石咪唑酯骨架材料(ZIFs)、莱瓦希尔骨架材料(MILs)、孔/通道式骨架材料(PCNs)等;归纳了聚合物基MOFs复合材料常用的两种制备方法,即物理共混法和原位法;总结了聚合物与MOFs间的复合方式,主要有非共价键复合和共价键复合。非共价键复合包括氢键、范德华力、静电作用等;共价键复合主要是氨基与羧基间的复合。在非共价键复合和共价键复合中都有氢键的作用,并且通过共价键可以使聚合物和MOFs材料更好地复合,从而使聚合物基MOFs复合材料更加稳定,应用更加广泛。最后介绍了聚合物基MOFs复合材料在生物医药、传感、气体分离膜等方面的应用现状,并对聚合物基MOFs复合材料的发展趋势进行了展望,主要包括复合材料的复合方式、复合材料的结构调控,以及复合材料在其他领域的应用。希望本文能为聚合物基MOFs复合材料方面的研究提供一定的指导与借鉴。     

多级孔金属有机骨架材料的合成及应用研究进展

通过对目前多级孔金属有机骨架材料MOFs的合成方法及其在吸附、催化、传感领域应用进行介绍与总结,对多级孔MOFs材料的合成方法与应用前景进行评述与展望。     

金属有机骨架材料固定化酶的研究进展

金属有机骨架材料(MOFs)凭借其较高的比表面积和孔体积、可设计和调控的孔径及结构,以及化学和热稳定性等特点,克服了传统固定化酶载体的孔径尺寸不可控、制备成本高、酶浸出、产物稳定性差等不足,近年来成为一类新型酶固定化载体.首先,本文分类总结了MOFs固定化酶的合成策略,包括后合成包装和从头合成封装(仿生矿化、共沉淀和机械化学封装);然后进一步介绍了多级孔MOFs的孔道设计策略及其固定化酶体系.这种具备分级孔道结构的MOFs用于固定化酶既可以保证酶的较高负载率,又能提高酶催化底物的扩散速率;此外,本文还介绍了MOFs共固定化多酶体系及具有类酶特性的仿生MOFs固定化酶方面的研究.MOFs特有的孔道结构可以大大缩短酶与底物之间的扩散距离,同时充分利用了酶级联反应的中间产物,可以显著提高酶催化活性;文章最后总结了MOFs固定化酶复合材料在生物传感和污染物催化净化领域的主要应用,提出了MOFs固定化酶研究中的一些瓶颈问题,以期为该材料的进一步研究和未来产业化提供借鉴和参考.     

金属-有机骨架材料的微波法制备及其应用

金属-有机骨架(MOFs)材料是一类由有机配体与金属中心经过自组装而形成的具有可调节孔径的材料。MOFs材料作为新功能材料,近年来成为研究的热点,在制备方法上有了很大的突破。采用微波法制得的MOFs材料与传统无机多孔材料相比,具有超大的比表面积和孔容积、可调的拓扑结构和孔径、良好的热稳定性等优点,因而在化学工业中有着广阔的应用前景,被广泛用于气体储存、催化、吸附等领域。对MOFs材料的微波法制备以及其应用进行了简单的介绍。     

Metal organic framework (MOF) in aqueous energy devices

Aqueous energy devices are under the spotlight of current research due to their safety, low cost and ease of handling. Metal-organic frameworks (MOFs) and their derivatives have spurred extensive exploration as they provide a library of new electrode materials. The rich and structural flexibilities (such as metal nodes, ligands, pore structure) endow MOFs and MOFs-derivatives with vast opportunities for various energy devices. In this review, we discuss the correlation between MOF structural parameters and electrochemical performance for aqueous energy devices in the scope of zinc-based batteries (Zn-ion, Zn-alkaline and Zn-air batteries), potassium-ion batteries and supercapacitors. For each energy device, the effect of determinative factors and structural modulating strategies of MOFs and derivatives are highlighted. Finally, we summarize the challenges and provide our perspective about MOFs and derivatives for future aqueous energy devices.     

Hydrogen Storage in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) are highly attractive materials because of their ultra‐high surface areas, simple preparation approaches, designable structures, and potential applications. In the past several years, MOFs have attracted worldwide attention in the area of hydrogen energy, particularly for hydrogen storage. In this review, the recent progress of hydrogen storage in MOFs is presented. The relationships between hydrogen capacities and structures of MOFs are evaluated, with emphasis on the roles of surface area and pore size. The interaction mechanism between H₂ and MOFs is discussed. The challenges to obtain a high hydrogen capacity at ambient temperature are explored.     

Recent Progress on Microfine Design of Metal–Organic Frameworks: Structure Regulation and Gas Sorption and Separation

Metal–organic frameworks (MOFs) have emerged as an important and unique class of functional crystalline hybrid porous materials in the past two decades. Due to their modular structures and adjustable pore system, such distinctive materials have exhibited remarkable prospects in key applications pertaining to adsorption such as gas storage, gas and liquid separations, and trace impurity removal. Evidently, gaining a better understanding of the structure–property relationship offers great potential for the enhancement of a given associated MOF property either by structural adjustments via isoreticular chemistry or by the design and construction of new MOF structures via the practice of reticular chemistry. Correspondingly, the application of isoreticular chemistry paves the way for the microfine design and structure regulation of presented MOFs. Explicitly, the microfine tuning is mainly based on known MOF platforms, focusing on the modification and/or functionalization of a precise part of the MOF structure or pore system, thus providing an effective approach to produce richer pore systems with enhanced performances from a limited number of MOF platforms. Here, the latest progress in this field is highlighted by emphasizing the differences and connections between various methods. Finally, the challenges together with prospects are also discussed.     

磁性金属有机复合材料的合成与应用

金属有机框架材料(MOFs)是一种将金属离子中心与有机配体通过配位键结合起来的一类具有网格结构的材料。由于金属离子以及有机配体的多样性,MOFs的结构也具有多样性。磁性金属有机复合材料是一种新型的复合材料,既结合了MOFs的网状结构及结构多变性的优点,又结合了磁性材料易于分离且可重复利用的特性,使得这种材料在药物载体、多相催化、选择吸附等多种方面都有着较为广泛的应用。以经典的几类MOFs为分类依据,研究了它们与磁性材料结合形成新型复合材料的方法,同时概括了这些新型复合材料在不同领域的应用,最后提出了该材料目前所存在的问题,并对今后的研究方向进行了展望。     

Construction of Hierarchical Metal–Organic Frameworks by Competitive Coordination Strategy for Highly Efficient CO2 Conversion

Hierarchical porosity and functionalization help to fully make use of metal–organic frameworks (MOFs) for their diverse applications. Herein, a simple strategy is reported to construct hierarchically porous MOFs through a competitive coordination method using tetrafluoroborate (M(BF₄)_x, where M is metal site) as both functional sites and etching agents. The resulting MOFs have in situ formed defect‐mesopores and functional sites without sacrificing their structure stability. The formation mechanism of the defect‐mesopores is elucidated by a combination of experimental and first‐principles calculation method, indicating the general feasibility of this new approach. Compared with the original microporous counterparts, the new hierarchical MOFs exhibit superior adsorption for the bulky dye molecules and catalytic performance for the CO₂ conversion attributed to their specific hierarchical pore structures.     

金属有机骨架材料在光催化反应中的应用研究进展

环境问题和能源危机的是当今人类社会面临的两大重要问题。光催化技术被认为是解决环境问题和能源危机的有效途径之一。光催化技术利用的关键就是光催化材料的开发。金属有机骨架材料(Metal-organic frameworks,MOFs)是由金属或金属簇与有机配体构筑的一类具有周期性网络结构的新型多孔晶体材料,具有比表面积大、孔道结构规整、孔尺寸可调、催化活性位丰富等优点,被广泛应用于气体存储、气体分离、多相催化、半导体、仿生矿化等多个领域。近十几年来,众多科研工作者尝试将MOFs材料用于光催化反应,并取得了许多优秀的科研成果。尤其是近几年,MOFs在光催化领域的应用受到了越来越多科研工作者的关注。主要综述了近几年MOFs作为光催化剂在催化产氢、CO_2还原、烷基化反应、有机物氧化、有机还原、交叉脱氢偶联反应和去除环境污染物等方面的应用研究进展,并对未来MOFs光催化材料的发展提出了建议。     

Optimization of the Pore Structures of MOFs for Record High Hydrogen Volumetric Working Capacity

Metal–organic frameworks (MOFs) are promising materials for onboard hydrogen storage thanks to the tunable pore size, pore volume, and pore geometry. In consideration of pore structures, the correlation between the pore volume and hydrogen storage capacity is examined and two empirical equations are rationalized to predict the hydrogen storage capacity of MOFs with different pore geometries. The total hydrogen adsorption under 100 bar and 77 K is predicted as n_tot= 0.085× V_p − 0.013× V_p² for cage-type MOFs and n_tot= 0.076× V_p − 0.011× V_p² for channel-type MOFs, where V_p is the pore volume of corresponding MOFs. The predictions by these empirical equations are validated by several MOFs with an average deviation of 5.4%. Compared with a previous equation for activated carbon materials, the empirical equations demonstrate superior accuracy especially for MOFs with high surface area (i.e., S_BET over ≈3000 m² g⁻¹). Guided by these empirical equations, a highly porous Zr-MOF NPF-200 (NPF: Nebraska Porous Framework) is examined to possess outstanding hydrogen total adsorption capacity (65.7 mmol g⁻¹) at 77 K and record high volumetric working capacity of 37.2 g L⁻¹ between 100 and 5 bar at 77 K.     

金属有机骨架材料质子传导的研究进展

金属有机骨架材料(MOFs)由于其结构多样性、骨架的可修饰性、超高比表面积和孔隙等特点,在质子传导、气体分离和吸附、催化、化学传感和生物医药领域有着独特的优势和广泛的应用。本文综述了近年来金属有机骨架材料在质子传导方面的研究进展,系统地阐述了质子传导的Grotthuss机理和Vehicel机理,并针对两种不同的机理分别总结了提高MOFs质子传导率的方法,对质子传导MOFs的设计具有显著的指导意义。此外,还介绍了质子传导MOFs最重要的应用之一——质子交换膜。质子交换膜由于其高电导率、易成膜以及优良的选择性透过等特点在燃料电池上有巨大的应用潜力。质子交换膜燃料电池的快速发展,可改善对化石燃料高度依赖的能源结构和日益恶化的环境问题。     

Alkylated Meso‐Macroporous Metal–Organic Framework Hollow Tubes as Nanocontainers of Octadecane for Energy Storage and Thermal Regulation

Alkylated meso‐macroporous Cr‐MIL‐101 hollow tubes (ACHT) are synthesized through the coordination of Cr³⁺ with alkylated bridged ligands. The alkylated ligands work as both bridging ligands and structure‐directing agents, which presents a new strategy for synthesizing meso‐macroporous metal–organic frameworks (MOFs). This is the first example of 1D meso‐macroporous MOF hollow tubes with large pore diameter (5–136 nm). Furthermore, the octadecane@ACHT form‐stable phase change materials (FSPCMs) are prepared using ACHT as nanocontainers for octadecane. The nanocavity of ACHT possesses enough storage space for octadecane, and the large number of alkyl chains on the ACHT framework induces octadecane molecules to crystallize from α‐ to β‐crystals. Considering the comfortable phase transition temperature (27.7 °C) and the relatively large thermal storage capacity (187 J g^?1), the octadecane@ACHT FSPCMs can be used in interior wall of building to improve the indoor thermal comfort or in the field of thermal‐regulated textiles and clothing.     

Mechanochemistry: Toward green synthesis of metal–organic frameworks

Metal–organic frameworks (MOFs) have attracted a special attention due to outstanding porosity, adjustable pore sizes, and huge opportunities in varying organic–inorganic compositions. Enormous studies conducted so far on MOFs indicate their high potential in catalysis, gas adsorption, drug delivery, water treatment, energy storage, among others. However, mass production of MOFs is still limited mainly due to the non-economic, non-green and complex synthesis methods. Mechanochemistry is an alternative solution for efficient and environmentally friendly syntheses of various MOFs. Fast and solvent-free or solvent-less mechanosynthesis seems to be a very powerful versatile method for obtaining these advanced porous materials. The mechanochemical concept was used for the preparation of various MOFs including the most popular structures: MOF-5, ZIF-8, HKUST-1, MIL-101, UiO-66. These MOFs feature high specific surface areas, comparable to those prepared by conventional solvent-based methods. Furthermore, mechanochemistry was successfully used for the synthesis of non-conventional multimetallic MOFs and previously unreported solid phases. This review shows the recent developments, challenges and perspectives of green synthesis of diverse MOF structures using mechanochemistry. Besides describing the mechanochemical synthesis of MOFs, some achievements in green applications are also summarized. Importantly, current trends in research suggests for further development of these fields i.e., harmful gas adsorption, water treatment, and energy storage.