Metal-organic Frameworks Research Articles

Reticular Chemistry for Enhancing Bioentity Stability and Functional Performance.

Addressing the fragility of bioentities that results in instability and compromised performance during storage and applications, reticular chemistry, specifically through metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), offers versatile platforms for stabilization and enhancement of bioentities. These highly porous frameworks facilitate efficient loading and mass transfer, offer confined environments and selective permeability for stabilization and protection, and enable finely tunable biointerfacial interactions and microenvironments for function optimization, significantly broadening the applications of various bioentities, including enzymes, nucleic acids, cells, etc. This Perspective outlines strategies for integrating bioentities with reticular frameworks, highlighting new design ideas for existing issues within these strategies. It emphasizes the crucial roles of these frameworks for bioentities in enhancing stability, boosting activity, imparting non-native functions, and synergizing bioentity systems. Concluding with a discussion of the challenges and prospects in the design, characterization, and practical applications of these biocomposites, this Perspective aims to inspire further development of high-performance biocomposites in this promising field.

Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites

The intricate hydrogen-bonded network of water gives rise to various structures with anomalous properties at different thermodynamic conditions. Nanoconfinement can further modify the water structure and properties, and induce specific water motifs, which are instrumental for technological applications such as atmospheric water harvesting. However, so far, a causal relationship between nanoconfinement and the presence of specific hydrophilic adsorption sites is lacking, hampering the further design of nanostructured materials for water templating. Therefore, this work investigates the organisation of water in zirconium-based metal-organic frameworks (MOFs) with varying topologies, pore sizes, and chemical composition, to extract design rules to shape water. The highly tuneable pores and hydrophilicity of MOFs makes them ideally suited for this purpose. We find that small nanopores favour orderly water clusters that nucleate at hydrophilic adsorption sites. Favourably positioning the secondary adsorption sites, hydrogen-bonded to the primary adsorption sites, allows larger clusters to form at moderate adsorption conditions. To disentangle the importance of nanoconfinement and hydrophilic nucleation sites in this process, we introduce an analytical model with precise control of the adsorption sites. This sheds a new light on design parameters to induce specific water clusters and hydrogen-bonded networks, thus rationalising the application space of water in nanoconfinement.

High-performance ammonia sensor at room temperature based on 2D conductive MOF Cu3(HITP)2

Sensitive detection of ammonia in the environment is crucial due to its potential danger to human ecology and health. In gas detection technology, resistive sensors utilizing golden cross finger electrodes combined with gas-sensitive materials are commonly employed. In this study, we demonstrated a room-temperature sensor for ambient ammonia detection. The sensor is composed of two-dimensional layer-stacked metal-organic framework (MOF) Cu3(HITP)2 nanomaterials drop-coated onto gold-forked finger electrodes. Density-functional theory simulation (DFT) and sensor gas-sensitive performance testing were conducted for characterization. The sensor exhibited high sensitivity, selectivity, low detection limit, excellent reproducibility, and stability. This can be attributed to the abundant Cu active sites exposed in the hexagonal ring and layer-stacked framework structure of Cu3(HITP)2 nanomaterials. Ammonia adsorption leads to electron transfer into the Cu3(HITP)2 framework, resulting in decreased sensor resistance. Real-time monitoring of sensor resistance changes enabled quantitative analysis. Results showed a 91.4 % response of the Cu3(HITP)2 sensor to 100 ppm NH3, with response and recovery times of 26 s and 20 s, respectively. The sensor's limit of detection (LOD) was approximately 15 ppb. The sensor exhibited a relatively high response to NH3 at 25 °C, as demonstrated by dynamic gradient test curves. These findings suggest that constituting a room-temperature ammonia sensor by uniformly drop-coating Cu3(HITP)2 onto a gold-forked finger electrode is a feasible strategy.

Location‐Specific Microenvironment Modulation Around Single‐Atom Metal Sites in Metal–Organic Frameworks for Boosting Catalysis

AbstractDespite coordination environment of catalytic metal sites has been recognized to be of great importance in single‐atom catalysts (SACs), a significant challenge remains in the understanding how the location‐specific microenvironment in the higher coordination sphere influences their catalysis. Herein, a series of Cu‐based SACs, namely Cu1/UiO‐66‐X (X=‐NO2, ‐H, and ‐NH2), are successfully constructed by anchoring single Cu atoms onto the Zr‐oxo clusters of metal–organic frameworks (MOFs), i.e., UiO‐66‐X. The ‐X functional groups dangling on the MOF linkers could be regarded as location‐specific remote microenvironment to regulate electronic properties of the single Cu atoms. Remarkably, they exhibit significant differences in the catalysis toward the hydroboration of alkynes. The activity follows the order of Cu1/UiO‐66‐NO2 > Cu1/UiO‐66 > Cu1/UiO‐66‐NH2 under identical reaction conditions, where Cu1/UiO‐66‐NO2 showcases the phenylacetylene conversion of 92 %, ~3.5 times higher efficiency than that of Cu1/UiO‐66‐NH2. Experimental and calculation results jointly support that the Cu electronic structure is modulated by the location‐specific microenvironment, thereby regulating the product desorption and promoting the catalysis.

Multifunctional Effect of Carbon Matrix with Sulfur Dopant Inspires Mixed Metal Sulfide as Freestanding Anode in Sodium-Ion Batteries.

As active materials for large-radius Na+ storage, metal sulfide (MS) anodes still face several challenges, including poor intrinsic electric conductivity, severe volume change along with the shuttle and dissolution effects of discharge-produced polysulfides. In this work, the mixed nickel-manganese sulfides (NiMnS) in the morphology of uniform 2D ultrathin nanosheets are derived from layered metal-organic frameworks (MOFs), where the NiS-MnS heterojunction are accommodated in carbon matrix with S dopant (NiMnS/SC). Through experiments and density functional theory (DFT) simulations, it is revealed that the carbon matrix with S dopant has multifunctional effects on active NiMnS during the charge/discharge process, including conductive intermediary, electrochemical active site, physical barrier, and chemical adsorption. This work may promote the design of MS-based electrodes in SIBs and extend the application of carbon material with S dopant in Na-S batteries.

Interfacial Microenvironment-Regulated Coordinate Structures Dictate the Metal-Organic Framework Facet Orientation toward Efficient CO2 Cycloaddition.

The preparation of high-quality highly oriented metal-organic framework (MOF) thin films is desirable for developing advanced functional devices. However, the pathways for controlling the oriented growth of MOFs are largely unknown, and determining their microcosmic evolution at the complex solid-liquid interface remains a challenge. Herein, we investigate the critical early growth stage of typical HKUST-1 on the COOH-functionalized Au substrate utilizing a combination of in situ surface-enhanced infrared spectroscopy, X-ray photoelectron spectroscopy, and photoinduced force microscopy. Detailed molecular level information indicates that it is not only the COOH-terminated SAM itself but also the distinct interfacial structures of the first metal coordinate layer and second ligand coordinate layer, which can be regulated in aprotic and protic solvents, that dominate the initial growth behavior of MOF and thus lead to the [111], [100], and polycrystal facet-oriented growth of HKUST-1. Moreover, the prepared HKUST-1 films exhibit a crystal facet-dependent catalytic rate in the chemical fixation of CO2 into cyclic carbonate. Our observations provide a reasonable guide for designing MOF-based anisotropic functional equipment.

Efficient Implementation of Monte Carlo Algorithms on Graphical Processing Units for Simulation of Adsorption in Porous Materials.

We present enhancements in Monte Carlo simulation speed and functionality within an open-source code, gRASPA, which uses graphical processing units (GPUs) to achieve significant performance improvements compared to serial, CPU implementations of Monte Carlo. The code supports a wide range of Monte Carlo simulations, including canonical ensemble (NVT), grand canonical, NVT Gibbs, Widom test particle insertions, and continuous-fractional component Monte Carlo. Implementation of grand canonical transition matrix Monte Carlo (GC-TMMC) and a novel feature to allow different moves for the different components of metal-organic framework (MOF) structures exemplify the capabilities of gRASPA for precise free energy calculations and enhanced adsorption studies, respectively. The introduction of a High-Throughput Computing (HTC) mode permits many Monte Carlo simulations on a single GPU device for accelerated materials discovery. The code can incorporate machine learning (ML) potentials, and this is illustrated with grand canonical Monte Carlo simulations of CO2 adsorption in Mg-MOF-74 that show much better agreement with experiment than simulations using a traditional force field. The open-source nature of gRASPA promotes reproducibility and openness in science, and users may add features to the code and optimize it for their own purposes. The code is written in CUDA/C++ and SYCL/C++ to support different GPU vendors. The gRASPA code is publicly available at https://github.com/snurr-group/gRASPA.

Design of Ligand‐Nonbridging Sites in Metal–Organic Frameworks for Boosting Lithium Storage Capacity

AbstractMetal–organic frameworks (MOFs) are lagging in the use of lithium‐ion batteries (LIBs), ascribing to full coordination between metal nodes and organic ligands, to a large extent. By integrating a modulator into a ligand with missing bridging functionality, this study elucidates the role of non‐bridging defect sites in MOFs in tailoring lithium storage performance. A fully bridged pristine MOF (p‐MOF) utilizing the meso‐tetra(4‐carboxylphenyl) porphyrin ligand is compared with a modified MOF containing non‐bridging defects (d‐MOF) introduced by a homologous ligand, tris(4‐carboxyphenyl) porphyrin. Spectroscopic and cryogenic low‐dose electron microscopy techniques verify the presence of non‐bridging defect sites in the d‐MOF and reveal their explicit local structure. Density functional theory calculations show significantly enhanced Li+ adsorption energies and reduced Li+ migration barriers at the non‐bridging sites in the d‐MOF compared to the fully bridging sites in the p‐MOF. As a result, the d‐MOF exhibits exceptional lithium storage performance, achieving a high capacity of 761 mAh g−1 at 0.05 A g−1 and superior rate performance of 203 mAh g−1 at 5 A g−1, which substantially outperform the p‐MOF. This study highlights the potential of modulating MOFs with non‐bridging defects to develop high‐performance LIBs.

An Ultrasensitive Self‐Calibrating Terbium Metal Organic Framework for the Detection of Amphotericin B

ABSTRACTWe successfully synthesized a 3D porous lanthanide metal–organic framework, [Tb (obdb)][Tb1/3(H2O)7/3]·NMP (Tb‐MOF) with hydrated terbium ions in the pores by solvothermal method using 4′,4″′‐oxybis[1,1′‐biphenyl]‐3,5‐dicarboxylic acid (H4obdb) as ligand. It is worth mentioning that Tb‐MOF exhibits excellent performance in structural stability and fluorescence response. Even after soaking in various solvents and pH solutions for 3 months, Tb‐MOF can maintain its structural integrity and excellent stability. The fluorescence spectra show that Tb‐MOF not only exhibits the luminescence of the ligand centered at 368 nm (IL), but also emits the characteristic emissions of the metal terbium, among which the luminescence at 542 nm is the strongest. In the detection of antibiotic amphotericin B (AB), Tb‐MOF showed significant detection efficiency. Upon increasing the concentration of AB, the fluorescence intensity at 542 nm gradually decreased, whereas the fluorescence at 368 nm decreased rapidly. The I542/IL value showed a very high linear correlation with AB concentration, with the slope reaching 1.29 × 108 M−1 (0–100 μM). In the field of fluorescent sensors for AB detection, Tb‐MOF is notable not only for its impressively low LOD (limt of detection) of 0.072 nM but also for pioneering the application of a self‐calibrating ratio‐based detection method. To better elucidate this fluorescence sensing phenomenon, we also conducted a detailed discussion of the sensing mechanism for AB.

Enhancing Durability of Organic–Inorganic Hybrid Perovskite Solar Cells in High‐Temperature Environments: Exploring Thermal Stability, Molecular Structures, and AI Applications

AbstractThe commercialization of perovskite solar cells (PSCs), as an emerging industry, still faces competition from other renewable energy technologies in the market. It is essential to ensure that PSCs are durable and stable in high‐temperature environments in order to meet the varied market demands of hot regions or seasons. The influence of high temperatures on the PSCs is complex, encompassing factors such as lattice strain, crystal phase changes, the creation of defects, and ion movement. Furthermore, it intensifies lattice vibrations and phonon scattering, which in turn impacts the migration rate of charge carriers. This review focuses on the durability of organic–inorganic hybrid PSCs under high temperatures. It begins by analyzing the impact of external temperature variations on the internal energy dynamics of PSCs. Subsequently, it outlines the various mechanisms provided by different functional molecules, applied to interface stabilization, grain boundary passivation, crystal growth control, electrode protection, and the development of new hole transport layers, to enhance the thermal stability of PSCs. Additionally, machine learning (ML) is discussed for predicting crystal structure stability, PSCs operational stability, and material screening, with a focus on the potential of deep learning and explainable artifical intelligence (AI) techniques in the commercialization of PSCs.

Synthesis of Homochiral N-Heterocyclic Carbene-Based Nanosheets for Enhanced Asymmetric Catalysis.

Utilizing ultrathin 2D metal-organic framework nanosheets (2D MONs) as supports for incorporating chiral catalysts represents a highly promising avenue in the field of asymmetric catalysis. In this study, four pairs of isostructural chiral metal-organic layers (MOLs) adorned with N-Heterocyclic carbene (NHC) groups are successfully synthesized. Notably, the obtained bulky (S)-1-Zn crystals can be readily delaminated into ultrathin MONs consisting of 1-2 layers through an ion intercalation-assisted exfoliation process. Subsequent asymmetric catalysis studies revealed that the NHC sites can be effectively activated by a proton sponge while maintaining structural integrity for the subsequent benzoin condensation. Due to their well-exposed catalytic sites, ultrathin morphology, and porous structure, the (S)-1-Zn nanosheets exhibited significantly enhanced yield and enantioselectivity compared to their bulk counterparts and organic precursors. This research highlights an efficient strategy for incorporating chiral NHC species onto 2D MONs, thereby unlocking their immense potential for heterogeneous asymmetric catalysis.

Fluoride Product Inhibition: New Insight into the Degradation of Nerve Agents by Zr-MOFs.

Zirconium-based metal-organic frameworks (Zr-MOFs) have shown remarkable efficacy in catalytically degrading neurotoxic agents in recent years. However, the catalytic activity of Zr-MOFs can be inhibited due to the binding of phosphate degradation products to the Zr nodes. Here, we reported the inhibition effect of a nonphosphate substance, fluoride, which can deactivate Zr-MOF nodes for the degradation of GD and VX and simulate DEPPT. The experimental and theoretical calculation results reveal that the fluoride product during GD degradation shows much more significant suppression than phosphate. The phosphate products can depart from the Zr nodes completely by adding H2O molecules on the Zr nodes to reduce the energy barrier. However, the fluoride can replace the bridged μ3-OH groups and terminal -OH groups on Zr-oxo clusters irreversibly, changing the electric density of Zr nodes and eliminating the terminal -OH. Without the terminal -OH, the five-coordinate phosphorus intermediate cannot be formed, resulting in the inactivation of Zr-O-Zr sites. This study provides new insights into Zr-MOF catalyst deactivation mechanisms and may help to develop a new strategy to design MOFs with high anti-inhibition efficiency for the degradation of nerve agents.

Multifaced Antifungal Activity of Dialdehyde Chitosan Loaded with Zinc Metal-Organic Framework (Zn-MOF)

Multifaced Antifungal Activity of Dialdehyde Chitosan Loaded with Zinc Metal-Organic Framework (Zn-MOF)

Enhanced gaseous benzene degradation by bimetallic MIL-101(Fe, Cu) activated persulfate system: Efficiency and mechanism

Persulfate oxidation is a promising technology for air pollution control but still suffers from degrading refractory volatile organic compounds (VOCs) under mild conditions. Metal-doped metal-organic frameworks (MOFs) offer a novel strategy to enhance persulfate activation and VOCs degradation. Herein, a novel bimetallic MIL-101 (Fe, Cu) is prepared for more effective degradation of gaseous benzene via persulfate activation. Under optimal conditions (Fe/Cu ratio of 1:4, persulfate concentration of 7 mM/L, pH of 5, and reaction temperature of 70 °C), the MIL-101(Fe1, Cu4) activated persulfate system achieves a benzene degradation efficiency of 79.1 %, a value significantly higher than that of MIL-101(Fe) (20.1 %). The enhanced performance can be attributed to the synergistic effect of Fe²⁺/Fe³⁺ and Cu²⁺/Cu⁺ redox interactions facilitating the activation of persulfate and generation of radical species. Density functional theory (DFT) calculations indicate an increase in the adsorption energy of MIL-101(Fe) in the presence of Cu doping from −3.46 eV to −5.92 eV along with a rise in the Fermi energy level from 0.5 eV to 1.33 eV, enhancing the electron density and mobility. A reaction energy diagram is provided to illustrate the reaction pathways and transition states involved in the degradation of benzene. Overall, the incorporation of Cu in MOFs significantly enhances the efficiency of persulfate-based oxidation systems toward VOCs degradation.

Peroxynitrite-Responsive Near-Infrared Fluorescent Imaging Guided Synergistic Chemo-Photodynamic Therapy via Biomimetic Metal-Organic Frameworks.

Peroxynitrite (ONOO-) plays a crucial role in maintaining cellular redox homeostasis and regulating diffusive processes, cellular transport, and signal transduction. Extensive studies have revealed that increased ONOO- levels during tumor progression are associated with heightened levels of oxidative stress. However, current methods lack noninvasive visualization, immediate reporting, and highly sensitive fluorescence sensing. In light of this, we have designed a biomimetic fluorescent nanoplatform, named Z-C-T@CM, for peroxynitrite-responsive near-infrared fluorescent imaging guided cancer treatment. The nanoplatform comprises tetrakis(4-carboxyphenyl) porphyrin (TCPP) and curcumin (CCM) encapsulated within a zeolitic imidazolate framework-8 (ZIF-8), which is coated with a mouse breast cancer cell membrane for enhanced biocompatibility and targeting, while evading immune clearance. In vitro experimental results demonstrate that the as-prepared nanoplatform exhibits enhanced near-infrared fluorescence emission upon exposure to ONOO-, indicating a significant potential for noninvasive in vivo imaging of ONOO- during tumor progression. Additionally, Z-C-T@CM readily degrades in the tumor microenvironment, releasing TCPP and CCM, enabling a synergistic chemo-photodynamic therapy with near-infrared illumination. Further investigations indicate that Z-C-T@CM efficiently stimulates a tumor immune response and facilitates therapeutic efficiency. Collectively, this work introduces a novel noninvasive strategy for ONOO- detection, shedding new light on the integration of cancer diagnosis and efficient treatment.

Copper Nanoclusters Imparted Metalloporphyrin Based Metal-Organic Frameworks for Enhanced CO2 Electroreduction.

Strategies that can introduce catalytic auxiliary into electrocatalysts to boost the performance of electrocatalytic CO2 reduction reaction (CO2RR) are meaningful in exploring hybrid electrocatalytic systems. Here, a series of hybrid electrocatalysts (Cu NCs@MOF-545-M, M=Fe, Co and Ni) have been prepared by assembly Cu NCs with MOF-545-M (M=Fe, Co and Ni) and successfully applied in electrocatalytic CO2RR. In the obtained MOF-545-M (M=Fe, Co and Ni), the integration of Cu NCs with MOF-545-M (M=Fe, Co and Ni) can create a hybrid electrocatalytic system that enhances the charge transfer efficiency and electrocatalytic CO2RR activity. Specifically, the optimal Cu NCs@MOF-545-Co presents remarkable FECO over a wide potential range (-0.7 V to -1.0 V), high CO generation rate (8.2 mol m-2 h-1) and excellent maximum energy efficiency (69 %, -0.7 V), which is superior to Cu NCs and MOF-545-Co, and represented to be one of the best performances to date. This work demonstrates a facile approach to significantly improve the FECO by loading metal nanoclusters into MOFs, providing a valuable reference for future studies on hybridization strategies to enhance the performance of electrocatalysts.

Enzyme-Free Identification of Monosaccharide Enantiomers on TiO2 Nanotube Array-Based Fabry-Pérot Interferometer.

Chirality is a vital property across various domains, especially for biological activity. Herein, an enzyme-free sensing platform for monosaccharide enantiomer identification was developed by utilizing the Fabry-Pérot interferometer feature of TiO2 nanotube arrays modified with enantioselective metal-organic framework and glucose oxidase-mimicking Au NPs. In this design, optical property is monitored by reflective interferometric Fourier transform spectroscopy (RIFTS), a highly sensitive technique for detecting changes in the average refractive index within nanotubular structures. Using glucose (Glu) enantiomers as the model targets, after the recognition of L-/d-Glu on mesoporous homochiral MIL-101 (Fe), Au NPs anchored in MIL-101(Fe) catalyze the oxidation of Glu molecules to produce hydrogen peroxide (H2O2). Benefiting from the confinement effect of frameworks, MIL-101(Fe), as an artificial enzyme with excellent peroxidase-like activity, catalyzes the conversion of 4-chloro-1-naphthol (4-CN) into insoluble precipitates. These gathered precipitates effectively change the average refractive index of the interferometric substrate. Based on the variation of effective optical thickness (ΔEOT) values, the enantioselective determination of l-Glu and d-Glu can be achieved. Moreover, the proposed RIFTS sensor also presents broad applicability for the identification of other monosaccharide enantiomers. As the enzyme-free homochiral interferometer is directly constructed on a Ti-metal sheet, the RIFTS platform offers a robust, sensitive, and low-cost device for monosaccharide enantiomer recognition.

EGCG-enabled Deep Tumor Penetration of Phosphatase and Acidity Dual-responsive Nanotherapeutics for Combinatory Therapy of Breast Cancer.

The presence of dense collagen fibers is a typical characteristic of triple-negative breast cancer (TNBC). Although these fibers hinder drug penetration and reduce treatment efficacy, the depletion of the collagen matrix is associated with tumor metastasis. To address this issue, epigallocatechin-3-gallate (EGCG) is first exploited for disrupting the dense collagenous stroma and alleviate fibrosis by specifically blocking the TGF-β/Smad pathway in fibroblasts and tumor cells when intraperitoneally administrated in TNBC tumor-bearing mice. A methotrexate (MTX)-loaded dual phosphate- and pH-responsive nanodrug (pHA@MOF-Au/MTX) is next engineered by integrating Fe-based metal-organic frameworks and gold nanoparticles for improved chemo/chemodynamic therapy of TNBC. Surface modification with pH (low)-insertion peptide substantially enhanced the binding of the nanodrug to 4T1 cells owing to tumor stroma remodeling by EGCG. High-concentration EGCG inhibited glutathione peroxidase by regulating mitochondrial glutamine metabolism, thus facilitating tumor cell ferroptosis. Furthermore, sequential EGCG and pHA@MOF-Au/MTX treatment showed remarkable anti-tumor effects in a mouse model of TNBC, with a tumor growth inhibition rate of 79.9%, and a pulmonary metastasis rate of 96.8%. Altogether, the combination strategy developed in this study can improve the efficacy of chemo/chemodynamic therapy in TNBC and represents an innovative application of EGCG.

Precise Modification of Organic Cations to Enhance the Moisture Stability and Luminescence Efficiency of Mn-Based Halides.

Eco-friendly organic-inorganic hybrid metal halides (OIMHs) are widely recognized as promising candidates for next-generation semiconductor materials. However, achieving inherent moisture stability in OIMHs remains a significant challenge due to the highly hygroscopic nature of the halide structures. In response, a strategy to precisely modify the organic cation (18-ACE: 4,13-diaza-18-crown 6-ether) was developed by introducing hydrophobic benzyl groups into 18-ACE, forming a protective layer that enhances the moisture stability of the OIMHs. Specifically, benzyl groups were incorporated into 18-ACE to create 18-ACE-Bn, which was then used as an organic component to construct zero-dimensional Mn-based (18-ACE)MnBr4 and (18-ACE-Bn)MnBr4·H2O, exhibiting photoluminescence quantum yields (PLQYs) of 68.18% and 97.17%, respectively. Notably, (18-ACE-Bn)MnBr4·H2O demonstrates exceptional moisture stability compared to (18-ACE)MnBr4, retaining 97% of its initial PLQY even after 180 days of exposure to 70% relative humidity. Molecular dynamics and density functional theory calculations indicate that this superior stability is attributed to the terminal benzyl groups embedded within the inorganic framework, forming a compact structure with abundant weak interactions. Leveraging the unique spectral characteristics of (18-ACE-Bn)MnBr4·H2O, a high-performance WLED with a wide color gamut of 125.2% NTSC (National Television Standard Committee) was developed, highlighting its potential for backlight display applications.

Metal‐Organic Framework‐based Electrodes for Asymmetric Supercapacitors

Supercapacitors (SCs) are a promising electrochemical device in the field of electrochemical energy storage, but their wide range applications are limited by relatively low energy density. Asymmetric supercapacitors (ASCs) based on different positive and negative electrodes offer the possibility to increase the energy density by extending the voltage window. It is essential to explore novel electrode materials to boost the electrochemical properties of ASCs. Metal‐organic frameworks (MOFs) have emerged as ideal electrode materials for SCs, due to their high porosity, tunable structure and highly dispersed active sites. MOFs can also be used as templates or precursors for the preparation of versatile electrode materials, such as carbon materials and metal compounds. In this minireview, SCs and MOF‐based electrode materials are first introduced, followed by an overview of recent advances in the synthesis of MOF‐based electrode materials including pristine MOFs, MOF derivatives and their composites, and their applications in ASCs acted as negative electrode, positive electrode or both. Finally, the challenges and prospects of MOF‐based ASCs are discussed.