Imparting Designer Biorecognition Functionality to Metal–Organic Frameworks by a DNA‐Mediated Surface Engineering Strategy

Surface functionality is an essential component for processing and application of metal–organic frameworks (MOFs). A simple and cost‐effective strategy for DNA‐mediated surface engineering of zirconium‐based nanoscale MOFs (NMOFs) is presented, capable of endowing them with specific molecular recognition properties and thus expanding their potential for applications in nanotechnology and biotechnology. It is shown that efficient immobilization of functional DNA on NMOFs can be achieved via surface coordination chemistry. With this strategy, it is demonstrated that such porphyrin‐based NMOFs can be modified with a DNA aptamer for targeting specific cancer cells. Furthermore, the DNA–NMOFs can facilitate the delivery of therapeutic DNA (e.g., CpG) into cells for efficient recognition of endosomal Toll‐like receptor 9 and subsequent enhanced immunostimulatory activity in vitro and in vivo. No apparent toxicity is observed with systemic delivery of the DNA–NMOFs in vivo. Overall, these results suggest that the strategy allows for surface functionalization of MOFs with different functional DNAs, extending the use of these materials to diverse applications in biosensor, bioimaging, and 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.     

Metal-organic framework-based intelligent drug delivery systems for cancer theranostic: A review

The design and development of multifunctional nano-drug delivery systems (NDDSs) is a solution that is expected to solve some intractable problems in traditional cancer treatment. In particular, metal-organic frameworks (MOFs) are novel hybrid porous nanomaterials which are constructed by the coordination of metal cations or clusters and organic bridging ligands. Benefiting from their intrinsic superior properties, MOFs have captivated intensive attentions in drug release and cancer theranostic. Based on what has been achieved about MOF-based DDSs in recent years, this review introduces different stimuli-responsive mechanisms of them and their applications in cancer diagnosis and treatment systematically. Moreover, the existing challenges and future opportunities in this field are summarized. By realizing industrial production and paying attention to biosafety, their clinical applications will be enriched.     

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.     

Engineering Homochiral Metal‐Organic Frameworks for Heterogeneous Asymmetric Catalysis and Enantioselective Separation

Owing to the potential applications in technological areas such as gas storage, catalysis, separation, sensing and nonlinear optics, tremendous efforts have been devoted to the development of porous metal‐organic frameworks (MOFs) over the past ten years. Homochiral porous MOFs are particularly attractive candidates as heterogeneous asymmetric catalysts and enantioselective adsorbents and separators for production of optically active organic compounds due to the lack of homochiral inorganic porous materials such as zeolites. In this review, we summarize the recent research progress in homochiral MOF materials, including their synthetic strategy, distinctive structural features and latest advances in asymmetric heterogeneous catalysis and enantioselective separation.     

Metal‐Organic Frameworks: Metal‐Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials (Adv. Mater. 2/2011)

Metal‐organic frameworks (MOFs) represent a new class of hybrid organic‐inorganic supramolecular materials comprised of ordered networks formed from organic electron donor linkers and metal cations. They can exhibit extremely high surface areas, as well as tunable pore size and functionality, and can act as hosts for a variety of guest molecules. Since their discovery, MOFs have enjoyed extensive exploration, with applications ranging from gas storage to drug delivery to sensing. This review covers advances in the MOF field from the past three years, focusing on applications, including gas separation, catalysis, drug delivery, optical and electronic applications, and sensing. We also summarize recent work on methods for MOF synthesis and computational modeling.     

Mesoporous Metal–Organic Frameworks: Synthetic Strategies and Emerging Applications

Metal–organic frameworks (MOFs) have attracted much attention over the past two decades due to their highly promising applications not only in the fields of gas storage, separation, catalysis, drug delivery, and sensors, but also in relatively new fields such as electric, magnetic, and optical materials resulting from their extremely high surface areas, open channels and large pore cavities compared with traditional porous materials like carbon and inorganic zeolites. Particularly, MOFs involving pores within the mesoscopic scale possess unique textural properties, leading to a series of research in the design and applications of mesoporous MOFs. Unlike previous Reviews, apart from focusing on recent advances in the synthetic routes, unique characteristics and applications of mesoporous MOFs, this Review also mentions the derivatives, composites, and hierarchical MOF‐based systems that contain mesoporosity, and technical boundaries and challenges brought by the drawbacks of mesoporosity. Moreover, this Review subsequently reveals promising perspectives of how recently discovered approaches to different morphologies of MOFs (not necessarily entirely mesoporous) and their corresponding performances can be extended to minimize the shortcomings of mesoporosity, thus providing a wider and brighter scope of future research into mesoporous MOFs, but not just limited to the finite progress in the target substances alone.     

Metal–Organic Framework‐Derived Materials for Sodium Energy Storage

Recently, sodium‐ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium‐ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal–organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF‐derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium‐ion storage performances of MOF‐derived materials, including MOF‐derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF‐derived materials in electrochemical energy storage are discussed.     

MOF‐Derived Metal Oxide Composites for Advanced Electrochemical Energy Storage

Over the past two decades, metal–organic frameworks (MOFs), a type of porous material, have aroused great interest as precursors or templates for the derivation of metal oxides and composites for the next generation of electrochemical energy storage applications owing to their high specific surface areas, controllable structures, and adjustable pore sizes. The electrode materials, which affect the performance in practical applications, are pivotal components of batteries and supercapacitors. Metal oxide composites derived from metal–organic frameworks possessing high reversible capacity and superior rate and cycle performance are excellent electrode materials. In this Review, potential applications for MOF‐derived metal oxide composites for lithium‐ion batteries, sodium‐ion batteries, lithium–oxygen batteries, and supercapacitors are studied and summarized. Finally, the challenges and opportunities for future research on MOF‐derived metal oxide composites are proposed on the basis of academic knowledge from the reported literature as well as from experimental experience.     

Metal–Organic Frameworks for Biomedical Applications

Metal–organic frameworks (MOFs) are an interesting and useful class of coordination polymers, constructed from metal ion/cluster nodes and functional organic ligands through coordination bonds, and have attracted extensive research interest during the past decades. Due to the unique features of diverse compositions, facile synthesis, easy surface functionalization, high surface areas, adjustable porosity, and tunable biocompatibility, MOFs have been widely used in hydrogen/methane storage, catalysis, biological imaging and sensing, drug delivery, desalination, gas separation, magnetic and electronic devices, nonlinear optics, water vapor capture, etc. Notably, with the rapid development of synthetic methods and surface functionalization strategies, smart MOF‐based nanocomposites with advanced bio‐related properties have been designed and fabricated to meet the growing demands of MOF materials for biomedical applications. This work outlines the synthesis and functionalization and the recent advances of MOFs in biomedical fields, including cargo (drugs, nucleic acids, proteins, and dyes) delivery for cancer therapy, bioimaging, antimicrobial, biosensing, and biocatalysis. The prospects and challenges in the field of MOF‐based biomedical materials are also discussed.     

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.     

Thermally Stable Metal‐Organic Framework‐Templated Synthesis of Hierarchically Porous Metal Sulfides: Enhanced Photocatalytic Hydrogen Production

Porous nanostructured materials are demonstrated to be very promising in catalysis due to their well accessible active sites. Thermally stable metal‐organic frameworks (MOFs) as hard templates are successfully utilized to afford porous metal oxides and subsequently metal sulfides by a nanocasting method. The resultant metal oxides/sulfides show considerable Brunauer–Emmett–Teller (BET) surface areas, by partially inheriting the pore character of MOF templates. Preliminary investigation on the obtained hierarchically porous CdS for water splitting, as a proof of concept, demonstrates its much higher activity than both corresponding bulk and nanosized counterparts, under visible light irradiation. Given the structural diversity and tailorability of MOFs, such synthetic approach may open an avenue to the synthesis of advanced porous materials for functional 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.     

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.     

Recent Progress in Metal‐Free Covalent Organic Frameworks as Heterogeneous Catalysts

Covalent organic frameworks (COFs), connecting different organic units into one system through covalent bonds, are crystalline organic porous materials with 2D or 3D networks. Compared with conventional porous materials such as inorganic zeolite, active carbon, and metal‐organic frameworks, COFs are a new type of porous materials with well‐designed pore structure, high surface area, outstanding stability, and easy functionalization at the molecular level, which have attracted extensive attention in various fields, such as energy storage, gas separation, sensing, photoluminescence, proton conduction, magnetic properties, drug delivery, and heterogeneous catalysis. Herein, the recent advances in metal‐free COFs as a versatile platform for heterogeneous catalysis in a wide range of chemical reactions are presented and the synthetic strategy and promising catalytic applications of COF‐based catalysts (including photocatalysis) are summarized. According to the types of catalytic reactions, this review is divided into the following five parts for discussion: achiral organic catalysis, chiral organic conversion, photocatalytic organic reactions, photocatalytic energy conversion (including water splitting and the reduction of carbon dioxide), and photocatalytic pollutant degradation. Furthermore, the remaining challenges and prospects of COFs as heterogeneous catalysts are also presented.     

Applications of Metal–Organic‐Framework‐Derived Carbon Materials

Carbon materials derived from metal–organic frameworks (MOFs) have attracted much attention in the field of scientific research in recent years because of their advantages of excellent electron conductivity, high porosity, and diverse applications. Tremendous efforts are devoted to improving their chemical and physical properties, including optimizing the morphology and structure of the carbon materials, compositing them with other materials, and so on. Here, many kinds of carbon materials derived from metal–organic frameworks are introduced with a particular focus on their promising applications in batteries (lithium‐ion batteries, lithium–sulfur batteries, and sodium‐ion batteries), supercapacitors (metal oxide/carbon and metal sulfide/carbon), electrocatalytic reactions (oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction), water treatment (MOF‐derived carbon and other techniques), and other possible fields. To close, some existing problem and corresponding possible solutions are proposed based on academic knowledge from the reported literature, along with a great deal of experimental experience.     

Integration of Metal Nanoparticles into Metal–Organic Frameworks for Composite Catalysts: Design and Synthetic Strategy

Metal–organic frameworks (MOFs) are constructed by periodically alternate metal ions with organic ligands, which offer structural diversity and a wide range of interesting properties as an attractive classification of crystalline porous materials. Integration of MOFs with other size‐limited functional centers can supply new multifunctional composites, which exhibit both the properties of the components and new characteristics due to the combination of MOFs with the selected loadings. In recent years, integration of metal/metal oxide nanoparticles (MNPs) into MOFs to form the composite catalysts has attracted considerable attention due to the superior performance. In this review, the latest studies and up‐to‐date developments on the design and synthetic strategy of new MNP@MOF composite catalysts are specifically highlighted. Both the achievements and problems are evaluated and proposed, and the opportunities and challenges of MNP@MOF composite catalysts are discussed.     

Metal-organic frameworks: a rapidly growing class of versatile nanoporous materials

Metal-organic frameworks (MOFs) represent a new class of hybrid organic-inorganic supramolecular materials comprised of ordered networks formed from organic electron donor linkers and metal cations. They can exhibit extremely high surface areas, as well as tunable pore size and functionality, and can act as hosts for a variety of guest molecules. Since their discovery, MOFs have enjoyed extensive exploration, with applications ranging from gas storage to drug delivery to sensing. This review covers advances in the MOF field from the past three years, focusing on applications, including gas separation, catalysis, drug delivery, optical and electronic applications, and sensing. We also summarize recent work on methods for MOF synthesis and computational modeling.     

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.     

Magnetic Metal–Organic Frameworks: γ‐Fe2O3@MOFs via Confined In Situ Pyrolysis Method for Drug Delivery

A general one‐step in situ pyrolysis route for the construction of metal–organic frameworks encapsulating superparamagnetic γ‐Fe₂O₃ NPs dispersed in the confined cavities of MOFs homogeneously is described. The integration of γ‐Fe₂O₃ NPs or clusters into MOFs can endow these porous materials with superparamagnetic element. By the combination of the thermal stability of MOFs and pyrolysis of metal triacetylacetonate complex at matched conditions, the porous structure of MOFs are well maintained while the size‐induced superparamagnetic property of nano γ‐Fe₂O₃ is obtained. As a proof of concept, both the γ‐ Fe₂O₃@ZIF‐8 and γ‐Fe₂O₃@MIL‐53(Al) were successfully prepared, and the latter was chosen to demonstrate its potential drug delivery as a magnetic MOF.