Conformation‐Controlled Molecular Sieving Effects for Membrane‐Based Propylene/Propane Separation

Membrane‐based separation is poised to reduce the operation cost of propylene/propane separation; however, identifying a suitable molecular sieve for membrane development is still an ongoing challenge. Here, the successful identification and use of a metal–organic framework (MOF) material as fillers, namely, the Zr‐fum‐ fcu ‐MOF possessing an optimal contracted triangular pore‐aperture driving the efficient diffusive separation of propylene from propane in mixed‐matrix membranes are reported. It is demonstrated that the fabricated hybrid membranes display a high propylene/propane separation performance, far beyond the current trade‐off limit of polymer membranes with excellent properties under industrial conditions. Most importantly, the mechanism behind the exceptional high propylene/propane selectivity is delineated by exploring theoretically the efficiency of sieving of different conformers of propane through the hypothesized triangular rigid pore‐aperture of Zr‐fum‐ fcu ‐MOF.     

Photothermal‐Responsive Microporous Nanosheets Confined Ionic Liquid for Efficient CO2 Separation

2D materials hold promising potential for novel gas separation. However, a lack of in‐plane pores and the randomly stacked interplane channels of these membranes still hinder their separation performance. In this work, ferrocene based‐MOFs (Zr‐Fc MOF) nanosheets, which contain abundant of in‐plane micropores, are synthesized as porous supports to fabricate Zr‐Fc MOF supported ionic liquid membrane (Zr‐Fc‐SILM) for highly efficient CO₂ separation. The micropores of Zr‐Fc MOF nanosheets not only provide extra paths for CO₂ transportation, and thus increase its permeance up to 145.15 GPU, but also endow the Zr‐Fc‐SILM with high selectivity (216.9) of CO₂/N₂ through the nanoconfinement effect, which is almost ten times higher than common porous polymer SILM. Furthermore, based on the photothermal‐responsive properties of Zr‐Fc MOF, the performance is further enhanced (35%) by light irradiation through a photothermal heating process. This provides a brand new way to design light facilitating gas separation membranes.     

Flexible Metal–Organic Framework‐Based Mixed‐Matrix Membranes: A New Platform for H2S Sensors

Metal–organic framework (MOF)–polymer mixed‐matrix membranes (MMMs) have shown great potential and superior performance in gas separations. However, their sensing application has not been fully established yet. Herein, a rare example of using flexible MOF‐based MMMs as a fluorescent turn‐on sensor for the detection of hydrogen sulfide (H₂S) is reported. These MOF‐based MMMs are readily prepared by mixing a highly stable aluminum‐based nano‐MOF (Al‐MIL‐53‐NO₂) into poly(vinylidene fluoride) with high loadings up to 70%. Unlike the intrinsic fragility and poor processability of pure‐MOF membranes, these MMMs exhibit desirable flexibility and processability that are more suitable for practical sensing applications. The uniform distribution of Al‐MIL‐53‐NO₂ particles combined with the permanent pores of MOFs enable these MMMs to show good water permeation flux and consequently have a full contact between the analyte and MOFs. The developed MMM sensor (70% MOF loading) thus shows a highly remarkable detection selectivity and sensitivity for H₂S with an exceptionally low detection limit around 92.31 × 10^?9m , three orders of magnitude lower than the reported powder‐form MOFs. This work demonstrates that it is feasible to develop flexible luminescent MOF‐based MMMs as a novel platform for chemical sensing applications.     

Separation of Chemical Reaction Intermediates by Metal–Organic Frameworks

HPLC columns custom‐packed with metal–organic framework (MOF) materials are used for the separation of four small intermediates and byproducts found in the commercial synthesis of an important active pharmaceutical ingredient in methanol. In particular, two closely related amines can be separated in the methanol reaction medium using MOFs, but not with traditional C18 columns using an optimized aqueous mobile phase. Infrared spectroscopy, UV–vis spectroscopy, X‐ray diffraction, and thermogravimetric analysis are used in combination with molecular dynamic simulations to study the separation mechanism for the best‐performing MOF materials. It is found that separation with ZIF‐8 is the result of an interplay between the thermodynamic driving force for solute adsorption within the framework pores and the kinetics of solute diffusion into the material pores, while the separation with Basolite F300 is achieved because of the specific interactions between the solutes and Fe³⁺ sites. This work, and the exceptional ability to tailor the porous properties of MOF materials, points to prospects for using MOF materials for the continuous separation and synthesis of pharmaceutical compounds.     

Emerging Multifunctional Metal–Organic Framework Materials

Metal?organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self‐assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre‐designing or post‐synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.     

Specific K+ Binding Sites as CO2 Traps in a Porous MOF for Enhanced CO2 Selective Sorption

Metal–organic frameworks (MOFs) can be fine‐tuned to boost sorbent‐sorbate interactions in order to improve gas sorption and separation performance, but the design of MOFs with ideal structural features for gas separation applications remains a challenge. Herein it is reported that unsaturated alkali metal sites can be immobilized in MOFs through a tetrazole based motif and that gas affinity can thereby be boosted. In the prototypal MOF of this type‐ NKU‐521 (NKU denotes Nankai University), K⁺ cations are effectively embedded in a trinuclear Co²⁺‐tetrazole coordination motif. The embedded K⁺ sites are exposed to the pores of NKU‐521 through water removal, and the isosteric heat (Q_st) for CO₂ is boosted to 41 kJ mol^‐1. The nature of the binding site is validated by molecular simulations and structural characterization. The K⁺ cations in effect serve as gas traps and boost the CO₂‐framework affinity, as measured by the Q_st, by 24%. In addition, the impact of unsaturated alkali metal sites upon the separation of hydrocarbons is evaluated for the first time in MOFs using ideal adsorbed solution theory (IAST) calculations and column breakthrough experiments. The results reveal that the presence of exposed K⁺ sites benefits gas sorption and hydrocarbon separation performances of this MOF.     

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.     

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.     

Nanosheets of Nonlayered Aluminum Metal–Organic Frameworks through a Surfactant‐Assisted Method

During the last decade, the synthesis and application of metal–organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom‐up surfactant‐assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant‐assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al‐containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.     

Highly Adsorptive,MOF‐Functionalized Nonwoven Fiber Mats for Hazardous Gas Capture Enabled by Atomic Layer Deposition

While metal‐organic frameworks (MOFs) show great potential for gas adsorption and storage, their powder form limits deployment opportunities. Integration of MOFs on polymeric fibrous scaffolds will enable new applications in gas adsorption, membrane separation, catalysis, and toxic gas sensing. Here, we demonstrate a new synthesis route for growing MOFs on fibrous materials that achieves high MOF loadings, large surface areas and high adsorptive capacities. We find that a nanoscale coating of Al₂O₃ formed by atomic layer deposition (ALD) on the surface of nonwoven fiber mats facilitates nucleation of MOFs on the fibers throughout the mat. Functionality of MOFs is fully maintained after integration, and MOF crystals are well attached to the fibers. Breakthrough tests for HKUST‐1 MOFs [Cu₃(BTC)₂] on ALD‐coated polypropylene fibers reveal NH₃ dynamic loadings up to 5.93 ± 0.20 mol/kg_(MOF+fiber). Most importantly, this synthetic approach is generally applicable to a wide range of polymer fibers (e.g., PP, PET, cotton) and MOFs (e.g., HKUST‐1, MOF‐74, and UiO‐66).     

Restricting Lattice Flexibility in Polycrystalline Metal–Organic Framework Membranes for Carbon Capture

Although polycrystalline metal‐organic framework (MOF) membranes offer several advantages over other nanoporous membranes, thus far they have not yielded good CO₂ separation performance, crucial for energy‐efficient carbon capture. ZIF‐8, one of the most popular MOFs, has a crystallographically determined pore aperture of 0.34 nm, ideal for CO₂/N₂ and CO₂/CH₄ separation; however, its flexible lattice restricts the corresponding separation selectivities to below 5. A novel postsynthetic rapid heat treatment (RHT), implemented in a few seconds at 360 °C, which drastically improves the carbon capture performance of the ZIF‐8 membranes, is reported. Lattice stiffening is confirmed by the appearance of a temperature‐activated transport, attributed to a stronger interaction of gas molecules with the pore aperture, with activation energy increasing with the molecular size (CH₄ > CO₂ > H₂). Unprecedented CO₂/CH₄, CO₂/N₂, and H₂/CH₄ selectivities exceeding 30, 30, and 175, respectively, and complete blockage of C₃H₆, are achieved. Spectroscopic and X‐ray diffraction studies confirm that while the coordination environment and crystallinity are unaffected, lattice distortion and strain are incorporated in the ZIF‐8 lattice, increasing the lattice stiffness. Overall, RHT treatment is a facile and versatile technique that can vastly improve the gas‐separation performance of the MOF membranes.     

Metal-Organic Frameworks for Greenhouse Gas Applications

Using petrol to supply energy for a car or burning coal to heat a building generates plenty of greenhouse gas (GHG) emissions, including carbon dioxide (CO₂), water vapor (H₂O), methane (CH₄), nitrous oxide (N₂O), ozone (O₃), fluorinated gases. These up-and-coming metal-organic frameworks (MOFs) are structurally endowed with rigid inorganic nodes and versatile organic linkers, which have been extensively used in the GHG-related applications to improve the lives and protect the environment. Porous MOF materials and their derivatives have been demonstrated to be competitive and promising candidates for GHG separation, storage and conversions as they shows facile preparation, large porosity, adjustable nanostructure, abundant topology, and tunable physicochemical property. Enormous progress has been made in GHG storage and separation intrinsically stemmed from the different interaction between guest molecule and host framework from MOF itself in the recent five years. Meanwhile, the use of porous MOF materials to transform GHG and the influence of external conditions on the adsorption performance of MOFs for GHG are also enclosed. In this review, it is also highlighted that the existing challenges and future directions are discussed and envisioned in the rational design, facile synthesis and comprehensive utilization of MOFs and their derivatives for 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.     

Super‐Stable,Highly Efficient,and Recyclable Fibrous Metal–Organic Framework Membranes for Precious Metal Recovery from Strong Acidic Solutions

Precious metals such as palladium (Pd) and platinum (Pt) are marvelous materials in the fields of electronic and catalysis, but they are tapering day by day. Zr(IV)‐based metal–organic frameworks (MOFs) are competent for their recovery, notably in harsh environments, while the general powder form limits their practical application. Porous MOF‐based membranes with ultraefficient metal ion permeation, strong stability, and high selectivity are, therefore, strikingly preferred. Herein, a set of polymeric fibrous membranes incorporated with the UiO‐66 series are fabricated; their adsorption/desorption capabilities toward Pd(II) and Pt(IV) are evaluated from strongly acidic solutions; and the MOF–polymer compatibilities are investigated. Polyurethane (PU)/UiO‐66‐NH₂ showed strong acid resistance and high chemical stability, which are attributable to strong π–π interactions between PU and MOF nanoparticles with a high configuration of energy. The as‐fabricated MOF membranes show extremely good adsorption/desorption performances without ruptures/coalitions of nanofibers or leak of MOF nanoparticles, and successfully display the efficacy in a gravity‐driven or even continuous‐flow system with good recycle performance and selectivity. The as‐fabricated MOF membranes set an example of potential MOF–polymer compatibility for practical applications.     

Integration of Biomolecules with Metal–Organic Frameworks

Owing to the progressive development of metal–organic‐frameworks (MOFs) synthetic processes and considerable potential applications in last decade, integrating biomolecules into MOFs has recently gain considerable attention. Biomolecules, including lipids, oligopeptides, nucleic acids, and proteins have been readily incorporated into MOF systems via versatile formulation methods. The formed biomolecule‐MOF hybrid structures have shown promising prospects in various fields, such as antitumor treatment, gene delivery, biomolecular sensing, and nanomotor device. By optimizing biomolecule integration methods while overcoming existing challenges, biomolecule‐integrated MOF platforms are very promising to generate more practical applications.     

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.     

Metal–Organic‐Framework‐Based Catalysts for Photoreduction of CO2

Photoreduction of CO₂ into reusable carbon forms is considered as a promising approach to address the crisis of energy from fossil fuels and reduce excessive CO₂ emission. Recently, metal–organic frameworks (MOFs) have attracted much attention as CO₂ photoreduction‐related catalysts, owing to their unique electronic band structures, excellent CO₂ adsorption capacities, and tailorable light‐absorption abilities. Recent advances on the design, synthesis, and CO₂ reduction applications of MOF‐based photocatalysts are discussed here, beginning with the introduction of the characteristics of high‐efficiency photocatalysts and structural advantages of MOFs. The roles of MOFs in CO₂ photoreduction systems as photocatalysts, photocatalytic hosts, and cocatalysts are analyzed. Detailed discussions focus on two constituents of pure MOFs (metal clusters such as Ti–O, Zr–O, and Fe–O clusters and functional organic linkers such as amino‐modified, photosensitizer‐functionalized, and electron‐rich conjugated linkers) and three types of MOF‐based composites (metal–MOF, semiconductor–MOF, and photosensitizer–MOF composites). The constituents, CO₂ adsorption capacities, absorption edges, and photocatalytic activities of these photocatalysts are highlighted to provide fundamental guidance to rational design of efficient MOF‐based photocatalyst materials for CO₂ reduction. A perspective of future research directions, critical challenges to be met, and potential solutions in this research field concludes the discussion.     

Rational Design of Catalytic Centers in Crystalline Frameworks

Crystalline frameworks including primarily metal organic frameworks (MOF) and covalent organic frameworks (COF) have received much attention in the field of heterogeneous catalysts recently. Beyond providing large surface area and spatial confinement, these crystalline frameworks can be designed to either directly act as or influence the catalytic sites at molecular level. This approach offers a unique advantage to gain deeper insights of structure–activity correlations in solid materials, leading to new guiding principles for rational design of advanced solid catalysts for potential important applications related to energy and fine chemical synthesis. In this review, recent key progress achieved in designing MOF‐ and COF‐based molecular solid catalysts and the mechanistic understanding of the catalytic centers and associated reaction pathways are summarized. The state‐of‐the‐art rational design of MOF‐ and COF‐based solid catalysts in this review is grouped into seven different areas: (i) metalated linkers, (ii) metalated moieties anchored on linkers, (iii) organic moieties anchored on linkers, (iv) encapsulated single sites in pores, and (v) metal‐mode‐based active sites in MOFs. Along with this, some attention is paid to theoretical studies about the reaction mechanisms. Finally, technical challenges and possible solutions in applying these catalysts for practical applications are also presented.     

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.     

Complex Nanostructures from Materials based on Metal–Organic Frameworks for Electrochemical Energy Storage and Conversion

Metal–organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF‐based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy‐related applications of complex nanostructures derived from MOF‐based precursors is provided. After a brief summary of synthetic methods of MOF‐based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single‐shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium‐ion batteries, hybrid supercapacitors, water‐splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF‐based‐templates for electrochemical energy storage and conversion applications are outlined.