An Overview of Metal–Organic Frameworks for Green Chemical Engineering

Given the current global energy and environmental issues resulting from the fast pace of industrialization, the discovery of new functional materials has become increasingly imperative in order to advance science and technology and address the associated challenges. The boom in metal–organic frameworks (MOFs) and MOF-derived materials in recent years has stimulated profound interest in exploring their structures and applications. The preparation, characterization, and processing of MOF materials are the basis of their full engagement in industrial implementation. With intensive research in these topics, it is time to promote the practical utilization of MOFs on an industrial scale, such as for green chemical engineering, by taking advantage of their superior functions. Many famous MOFs have already demonstrated superiority over traditional materials in solving real-world problems. This review starts with the basic concept of MOF chemistry and ends with a discussion of the industrial production and exploitation of MOFs in several fields. Its goal is to provide a general scope of application to inspire MOF researchers to convert their focus on academic research to one on practical applications. After the obstacles of cost, scale-up preparation, processability, and stability have been overcome, MOFs and MOF-based devices will gradually enter the factory, become a part of our daily lives, and help to create a future based on green production and green living.     

基于静电纺丝技术的聚合物基MOFs纳米纤维膜的研究进展

基于静电纺丝技术的金属有机骨架纳米纤维膜材料(Metal-Organic Frameworks Nanofibrous Membranes,MOFs NFMs)综合了无机多孔材料和聚合物纳米纤维的优势,是一类具有广阔应用前景的功能性材料.目前已经开发出不同功能的MOFs NFMs,其应用领域也在不断扩展.本文介绍了MO...     

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。     

Multifunctional Metal–Organic Frameworks for Photocatalysis

Metal–organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO₂ reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world‐wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF‐involved solar‐to‐chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co‐catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.     

Metal–Organic Framework‐Based Nanomedicine Platforms for Drug Delivery and Molecular Imaging

Metal–organic frameworks (MOFs), which are a unique class of hybrid porous materials built from metal ions and organic linkers, have attracted significant research interest in recent years. Compared with conventional porous materials, MOFs exhibit a variety of advantages, including a large surface area, a tunable pore size and shape, an adjustable composition and structure, biodegradability, and versatile functionalities, which enable MOFs to perform as promising platforms for drug delivery, molecular imaging, and theranostic applications. In this article, the recent research progress related to nanoscale metal–organic frameworks (NMOFs) is summarized with a focus on synthesis strategies and drug delivery, molecular imaging, and theranostic applications. The future challenges and opportunities of NMOFs are also discussed in the context of translational medical research. More effort is warranted to develop clinically translatable NMOFs for various applications in nanomedicine.     

Metal–Organic Framework (MOF)‐Based Drug/Cargo Delivery and Cancer Therapy

Metal–organic frameworks (MOFs)—an emerging class of hybrid porous materials built from metal ions or clusters bridged by organic linkers—have attracted increasing attention in recent years. The superior properties of MOFs, such as well‐defined pore aperture, tailorable composition and structure, tunable size, versatile functionality, high agent loading, and improved biocompatibility, make them promising candidates as drug delivery hosts. Furthermore, scientists have made remarkable achievements in the field of nanomedical applications of MOFs, owing to their facile synthesis on the nanoscale and alternative functionalization via inclusion and surface chemistry. A brief introduction to the applications of MOFs in controlled drug/cargo delivery and cancer therapy that have been reported in recent years is provided here.     

Patterning Techniques for Metal Organic Frameworks

The tuneable pore size and architecture, chemical properties and functionalization make metal organic frameworks (MOFs) attractive versatile stimuli‐responsive materials. In this context, MOFs hold promise for industrial applications and a fervent research field is currently investigating MOF properties for device fabrication. Although the material properties have a crucial role, the ability to precisely locate the functional material is fundamental for device fabrication. In this progress report, advancements in the control of MOF positioning and precise localization of functional materials within MOF crystals are presented. Advantages and limitations of each reviewed technique are critically investigated, and several important gaps in the technological development for device fabrication are highlighted. Finally, promising patterning techniques are presented which are inspired by previous studies in organic and inorganic crystal patterning for the future of MOF lithography.     

多色应力发光的镧系掺杂金属有机框架

金属有机框架(MOF)和应力发光(ML)材料被认为是两种有前途的材料,并在诸多领域得到了广泛应用.若能将二者结合起来获得ML-MOF材料,则势必会拓展它们的应用范围.但目前对MLMOF的研究并不多,且其中的ML机制仍不明确.在本研究中,我们提出了一种通过在非中心对称SBD MOF中掺杂镧系离子来开发ML-MOF的策略,...     

Hydrophobic Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have diverse potential applications in catalysis, gas storage, separation, and drug delivery because of their nanoscale periodicity, permanent porosity, channel functionalization, and structural diversity. Despite these promising properties, the inherent structural features of even some of the best‐performing MOFs make them moisture‐sensitive and unstable in aqueous media, limiting their practical usefulness. This problem could be overcome by developing stable hydrophobic MOFs whose chemical composition is tuned to ensure that their metal–ligand bonds persist even in the presence of moisture and water. However, the design and fabrication of such hydrophobic MOFs pose a significant challenge. Reported syntheses of hydrophobic MOFs are critically summarized, highlighting issues relating to their design, characterization, and practical use. First, wetting of hydrophobic materials is introduced and the four main strategies for synthesizing hydrophobic MOFs are discussed. Afterward, critical challenges in quantifying the wettability of these hydrophobic porous surfaces and solutions to these challenges are discussed. Finally, the reported uses of hydrophobic MOFs in practical applications such as hydrocarbon storage/separation and their use in separating oil spills from water are summarized. Finally, the state of the art is summarized and promising future developments of hydrophobic MOFs are highlighted.     

Hybridization of MOFs and COFs: A New Strategy for Construction of MOF@COF Core–Shell Hybrid Materials

The exploration of new porous hybrid materials is of great importance because of their unique properties and promising applications in separation of materials, catalysis, etc. Herein, for the first time, by integration of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), a new type of MOF@COF core–shell hybrid material, i.e., NH₂‐MIL‐68@TPA‐COF, with high crystallinity and hierarchical pore structure, is synthesized. As a proof‐of‐concept application, the obtained NH₂‐MIL‐68@TPA‐COF hybrid material is used as an effective visible‐light‐driven photocatalyst for the degradation of rhodamine B. The synthetic strategy in this study opens up a new avenue for the construction of other MOF–COF hybrid materials, which could have various promising applications.     

Metal–Organic Frameworks Based Nano/Micro/Millimeter‐Sized Self‐Propelled Autonomous Machines

Synthetic nano/micro/millimeter‐sized machines that harvest energy from the surrounding environment and then convert it to motion have had a significant impact on many research areas such as biology (sensing, imaging, and therapy) and environmental applications. Autonomous motion is a key element of these devices. A high surface area is preferable as it leads to increased propellant or cargo‐loading capability. Integrating highly ordered and porous metal–organic frameworks (MOFs) with self‐propelled machines is demonstrated to have a significant impact on the field of nano/micro/millimeter‐sized devices for a wide range of applications. MOFs have shown great potential in many research fields due to their tailorable pore size. These fields include energy storage and conversion; catalysis, biomedical application (e.g., drug delivery, imaging, and cancer therapy), and environmental remediation. The marriage of motors and MOFs may provide opportunities for many new applications for synthetic nano/micro/millimeter‐sized machines. Herein, MOF‐based micro‐ and nanomachines are reviewed with a focus on the specific properties of MOFs.     

Metal-organic frameworks: Challenges and opportunities for ion-exchange/sorption applications

Exposure to common ionic pollutants, such as heavy metal ions and toxic anions, is a major concern throughout the world due to their potential impacts on human health and the environment. Recently, metal-organic frameworks (MOFs) with ion-exchange properties have attracted great interest with respect to the capture of diverse hazardous cationic and anionic species. In fact, according to the investigations on these ion exchangers, their sorption capacities are recognized to be considerably superior to conventional materials. This review focused on metal-organic materials as sorbents for ions by surveying MOFs with respect to their exchange/sorption capacities in association with their synthesis and structural characteristics. We also described the recent development in MOF composites and their practical applications toward wastewater treatment. The sorption characteristics were also evaluated among the reported MOFs and then between MOFs and other sorbents. Finally, we described the future prospects for the research and development in materials for ion-exchange based on MOF technology.     

State‐of‐the‐Art Advances and Challenges of Iron‐Based Metal Organic Frameworks from Attractive Features,Synthesis to Multifunctional Applications

Metal organic frameworks (MOFs), as an original kind of organic–inorganic porous material, are constructed with metal centers and organic linkers via a coordination complexation reaction. Among uncountable MOF materials, iron‐containing metal organic frameworks (Fe‐MOFs) have excellent potential in practical applications owing to their many fascinating properties, such as diverse structure types, low toxicity, preferable stability, and tailored functionality. Here, recent research progresses of Fe‐MOFs in attractive features, synthesis, and multifunctional applications are described. Fe‐MOFs with porosity and tailored functionality are discussed according to the design of building blocks. Four types of synthetic methods including solvothermal, hydrothermal, microwave, and dry gel conversion synthesis are illustrated. Finally, the applications of Fe‐MOFs in Li‐ion batteries, sensors, gas storage, separation in gas and liquid phases, and catalysis are elucidated, focusing on the mechanism. The aim is to provide prospects for extending Fe‐MOFs in more practical applications.     

金属有机框架材料载体系统在食品抗菌包装中的应用

目的 综述金属有机框架材料(Metal-organic frameworks,MOFs)作为载体系统在食品抗菌包装领域的研究现状和应用进展,以期为MOFs类抗菌包装材料的研发和应用提供参考。方法 介绍MOFs的基本概念及分类,概述MOFs的制备方法(加热法、机械法和电化学法等),总结归纳近年来MOFs作为载体系统在无机抗菌剂、有机抗菌剂和天然抗菌剂领域的应用,并讨论MOFs作为载体系统的机遇和挑战。结论 MOFs作为一种有机与无机相结合的多孔性复合材料,不仅可有效封装抗菌剂,实现缓释和控释,且将MOFs复合材料作为高分子填料可提高其抗菌性能、力学性能和抗紫外线性能等,因此在制备高效、安全的食品抗菌包装方面具有巨大潜力。     

Interface-modulated fabrication of hierarchical yolk–shell Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/C dodecahedrons as stable anodes for lithium and sodium storage

Transition-metal oxides (TMOs) have gradually attracted attention from researchers as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of their high theoretical capacity.However,their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic conductivity limit their applications.To solve the problems of TMOs,carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks (MOFs) have emerged as promising electrode materials for LIBs and SIBs.In this study,we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imidazolate frameworks.This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process.The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation,and the carbon matrix improves the electrical conductivity of the electrode.As an anode for LIBs,the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability (1,100 mAh·g-1 after 120 cycles at 200 mA·g-1).As an anode for SIBs,the composites exhibit an outstanding rate capability (307 mAh·g-1 at 1,000 mA·g-1 and 269 mAh·g-1 at 2,000 mA·g-1).Detailed electrochemical kinetic analysis indicates that the energy storage for Li+ and Na+ in yolk-shell Co3O4/C dodecahedrons shows a dominant capacitive behavior.This work introduces an effective approach for fabricating carbonbased metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.     

Highly Stable Phosphonate-Based MOFs with Engineered Bandgaps for Efficient Photocatalytic Hydrogen Production

Photoactive metal–organic frameworks (MOFs) represent one of the most promising materials for photocatalytic hydrogen production, but phosphonate-based MOFs have remained largely underdeveloped compared to other conventional MOFs. Herein, a photocatalyst of 1D titanium phosphonate MOF is designed through an easy and scalable stirring hydrothermal method. Homogeneous incorporation of organophosphonic linkers can narrow the bandgap, which is due to the strong electron-donating ability of the  OH functional group that can efficiently shift the top of the valence band, moving the light absorption to the visible portion of the spectrum. In addition, the unique 1D nanowire topology enhances the photoinduced charge carrier transport and separation. Accordingly, the titanium phosphonate nanowires deliver remarkably enhanced photocatalytic hydrogen evolution activity under irradiation of both visible light and a full-spectrum simulator. Such concepts of engineering both nanostructures and electronic states herald a new paradigm for designing MOF-based photocatalysts.     

Metal-Organic Framework Materials in Perovskite Solar Cells: Recent Advancements and Perspectives

Organic–inorganic hybrid perovskite solar cells (PSCs) are among the most promising candidates for the next generation of photovoltaic devices because of the significant increase in their power conversion efficiency (PCE) from less than 10% to 25.7% in past decade. The metal-organic framework (MOF) materials owing to their unique properties, such as large specific surface area, abundant binding sites, adjustable nanostructures, and synergistic effects, are used as additives or functional layers to enhance the device performance and long-term stability of PSCs. This review focuses on the recent advancements in the applications of MOFs as/in different functional layers of PSCs. The photovoltaic performance, impact, and advantages of MOF materials integrated into the perovskite absorber, electron transport layer, hole transport layer, and interfacial layer are reviewed. In addition, the applicability of MOFs to mitigate leakage of Pb²⁺ from halide perovskites and corresponding devices is discussed. This review concludes with the perspectives on further research directions for employing MOFs in PSCs.     

导电金属有机骨架材料在超级电容器中的应用

随着电子技术的持续发展, 对供电设备的要求也相应提高。超级电容器(SCs)具有较高的能量密度和优异的功率输出性能, 是新一代小型化、智能化、可穿戴电子设备的理想供电装置。开发能够快速充放电、性能稳定的SCs产品是储能领域的研究重点。电极材料作为SCs最重要的组成部分, 是进一步提升其性能的关键。导电金属有机骨架(MOFs)作为新型SCs电极材料, 具有规整的孔道结构、大比表面积、多种形貌及维度、可调控的导电性能等优异性质, 展现出巨大的潜力并引起了广泛关注。本文结合SCs的储能机理, 介绍了导电MOFs的结构、制备及导电机制, 进一步阐述了其作为SCs电极材料的设计策略, 重点综述了其在SCs领域的研究进展, 并展望了其应用前景与发展方向。     

介孔材料可控合成及在核工业中的应用研究进展

介绍了介孔材料可控合成方法及研究进展,综述了介孔材料在核工业中的应用,如用于放射性核素的吸附、分离和废物固化等,并对介孔材料控制合成和应用前景进行了展望。提出应对介孔材料进行孔道结构及形貌控制合成、修饰或功能化研究,制备具有短孔道特殊形貌的介孔材料,提高其吸附性能和选择性;寻求更经济可行的合成路线,降低介孔材料的生产成本,逐步实现产业化;深入研究可控合成机理及介孔材料对放射性核素的吸附机理。     

Heterogeneous Catalysis in Zeolites,Mesoporous Silica,and Metal–Organic Frameworks

Crystalline porous materials are important in the development of catalytic systems with high scientific and industrial impact. Zeolites, ordered mesoporous silica, and metal–organic frameworks (MOFs) are three types of porous materials that can be used as heterogeneous catalysts. This review focuses on a comparison of the catalytic activities of zeolites, mesoporous silica, and MOFs. In the first part of the review, the distinctive properties of these porous materials relevant to catalysis are discussed, and the corresponding catalytic reactions are highlighted. In the second part, the catalytic behaviors of zeolites, mesoporous silica, and MOFs in four types of general organic reactions (acid, base, oxidation, and hydrogenation) are compared. The advantages and disadvantages of each porous material for catalytic reactions are summarized. Conclusions and prospects for future development of these porous materials in this field are provided in the last section. This review aims to highlight recent research advancements in zeolites, ordered mesoporous silica, and MOFs for heterogeneous catalysis, and inspire further studies in this rapidly developing field.