Metal-organic Frameworks Research Research Articles

The Road Ahead for Metal-Organic Frameworks: Current Landscape, Challenges and Future Prospects.

This perspective highlights the transformative potential of Metal-Organic Frameworks (MOFs) in environmental and healthcare sectors. It discusses work that has advanced beyond technology readiness levels of >4 including applications in capture, storage, and conversion of gases to value added products. This work showcases efforts in the most salient applications of MOFs which have been performed at a great cadence, enabled by the federal government, large companies, and startups to commercialize these technologies despite facing significant challenges. This article also forecasts the role of nanoscale MOFs in healthcare, including strides toward personalized medicine, advocating for their use in custom-tailored drug delivery systems. Finally we underscore the potential acceleration in MOF research and development through the integration of machine learning and AI, positioning MOFs as versatile tools poised to address global sustainability and health challenges.

MOFSynth: A Computational Tool toward Synthetic Likelihood Predictions of MOFs.

In the past decade, high-throughput computational studies of materials have increased significantly mainly due to advances in computer capabilities and have attracted a great deal of interest. In the field of metal-organic frameworks (MOFs), over a million hypothetical MOFs have been designed in silico, yet only a small fraction of these have been synthesized. For validating the computational-hypothetical results and accelerating the progress in the field, there is a pressing need for distinguishing MOFs that are more likely to be synthesized for real-life applications. This study presents a comprehensive investigation into the synthesizability likelihood of MOFs, utilizing a novel computational approach based on the disparities in energy and geometry between the linker conformation within the MOF structure and its isolated, free-gas state since both of these have been proven to be critical factors influencing MOF synthesis. Our user-friendly tool streamlines synthesizability evaluation, requiring minimal expertise in computational chemistry. By deconstructing over 40,000 MOFs from databases, including QMOF, CoRE MOF, and ToBaCCo, we analyze key parameters defining the linker strain within the MOF unit cell. Our results indicate that QMOF and CoRE MOF contain more promising candidates for synthesis, while ToBaCCo exhibits a relatively poor synthesizability likelihood due to unoptimized materials. Through extensive analysis, we identify optimal linker candidates for highly synthesizable MOFs. Consistent trends in energy distribution across databases that are confirmed by high Pearson and Spearman coefficients suggest the potential for omitting optimization calculations, significantly reducing computational costs. This study underscores the importance of linker deformation and energy disparities and enhances our understanding of synthetic accessibility in MOF research, offering valuable insights for future advancements in the field.

Metal-Organic Frameworks for Sustainable Crop Disease Management: Current Applications, Mechanistic Insights, and Future Challenges.

Efficient management of crop diseases and yield enhancement are essential for addressing the increasing food demands due to global population growth. Metal-organic frameworks (MOFs), which have rapidly evolved throughout the 21st century, are notable for their vast surface area, porosity, and adaptability, establishing them as highly effective vehicles for controlled drug delivery. This review methodically categorizes common MOFs employed in crop disease management and details their effectiveness against various pathogens. Additionally, by critically evaluating existing research, it outlines strategic approaches for the design of drug-delivery MOFs and explains the mechanisms through which MOFs enhance disease resistance. Finally, this paper identifies the current challenges in MOF research for crop disease management and suggests directions for future research. Through this in-depth review, the paper seeks to enrich the understanding of MOFs applications in crop disease management and offers valuable insights for researchers and practitioners.

Heavy metal sequestration from wastewater by metal-organic frameworks: a state-of-the-art review of recent progress.

Metal-organic frameworks (MOFs) have emerged as highly promising adsorbents for removing heavy metals from wastewater due to their tunable structures, high surface areas, and exceptional adsorption capacities. This review meticulously examines and summarizes recent advancements in producing and utilizing MOF-based adsorbents for sequestering heavy metal ions from water. It begins by outlining and contrasting commonly employed methods for synthesizing MOFs, such as solvothermal, microwave, electrochemical, ultrasonic, and mechanochemical. Rather than delving into the specifics of adsorption process parameters, the focus shifts to analyzing the adsorption capabilities and underlying mechanisms against critical metal(loid) ions like chromium, arsenic, lead, cadmium, and mercury under various environmental conditions. Additionally, this article discusses strategies to optimize MOF performance, scale-up production, and address environmental implications. The comprehensive review aims to enhance the understanding of MOF-based adsorption for heavy metal remediation and stimulate further research in this critical field. In brief, this review article presents a comprehensive overview of the contemporary information on MOFs as an effective adsorbent and the challenges being faced by these adsorbents for heavy metal mitigation (including stability, cost, environmental issues, and optimization), targeting to develop a vital reference for future MOF research.

Synthesis and application of metal-organic frameworks

Metal-organic frameworks (MOFs) are an intriguing class of materials that undergoes self-assembly, originating from polydentate organic ligands. These ligands are primarily composed of aromatic polynucleic acids and polybases, along with transition metal ions. The advancements in MOFs have diversified, employing ligands based on carboxylates or nitrogen-containing heterocyclic organic neutral ligands, resulting in materials characterized by their increased porosity and remarkable chemical stability. The research provides a comprehensive review of conventional and alternative synthesis methods, highlighting recent techniques such as microwave-assisted, electrochemical, mechanochemical, and sonochemical synthesis. The synthesis methods are discussed in detail, to provide a comprehensive understanding of the various techniques available. The versatile properties of MOFs find applications in various fields such as gas adsorption, chemical sensing, catalysis, and drug delivery. The analysis not only deepens the understanding of MOFs' present state but also inspires future innovations in their synthesis and applications. The research also highlights the potential of MOFs in drug delivery, where they can be used as carriers for the delivery of drugs or other therapeutic agents. The comprehensiveness of this research provides a valuable resource for understanding the current state of MOFs research and identifies future directions for innovation in their synthesis and applications.

Accelerating the practical application of MOFs for hydrogen storage—from performance-driven to application-oriented

Metal–organic frameworks (MOFs) are highly promising porous materials known for their exceptional porosity, extensive surface area, and customizable pore structures, making them an ideal solution for hydrogen storage. However, most MOFs research remains confined to the laboratory, lacking practical applications. To address this, the author proposes a shift towards practical applications, the creation of a comprehensive MOFs database, alignment of synthesis with practical considerations, and diversification of MOFs applications. These steps are crucial for harnessing the full potential of MOFs in real-world energy challenges.

Evaluation of Open-Source Large Language Models for Metal-Organic Frameworks Research.

Along with the development of machine learning, deep learning, and large language models (LLMs) such as GPT-4 (GPT: Generative Pre-Trained Transformer), artificial intelligence (AI) tools have been playing an increasingly important role in chemical and material research to facilitate the material screening and design. Despite the exciting progress of GPT-4 based AI research assistance, open-source LLMs have not gained much attention from the scientific community. This work primarily focused on metal-organic frameworks (MOFs) as a subdomain of chemistry and evaluated six top-rated open-source LLMs with a comprehensive set of tasks including MOFs knowledge, basic chemistry knowledge, in-depth chemistry knowledge, knowledge extraction, database reading, predicting material property, experiment design, computational scripts generation, guiding experiment, data analysis, and paper polishing, which covers the basic units of MOFs research. In general, these LLMs were capable of most of the tasks. Especially, Llama2-7B and ChatGLM2-6B were found to perform particularly well with moderate computational resources. Additionally, the performance of different parameter versions of the same model was compared, which revealed the superior performance of higher parameter versions.

Focused ion beam milling and MicroED structure determination of metal-organic framework crystals

We report new advancements in the determination and high-resolution structural analysis of beam-sensitive metal organic frameworks (MOFs) using microcrystal electron diffraction (MicroED) coupled with focused ion beam milling at cryogenic temperatures (cryo-FIB). A microcrystal of the beam-sensitive MOF, ZIF-8, was ion-beam milled in a thin lamella approximately 150 nm thick. MicroED data were collected from this thin lamella using an energy filter and a direct electron detector operating in counting mode. Using this approach, we achieved a greatly improved resolution of 0.59 Å with a minimal total exposure of only 0.64 e−/A2. These innovations not only improve model statistics but also further demonstrate that ion-beam milling is compatible with beam-sensitive materials, augmenting the capabilities of electron diffraction in MOF research.

Exploring the Structural, Dynamic, and Functional Properties of Metal‐Organic Frameworks through Molecular Modeling

AbstractThis review spotlights the role of atomic‐level modeling in research on metal‐organic frameworks (MOFs), especially the key methodologies of density functional theory (DFT), Monte Carlo (MC) simulations, and molecular dynamics (MD) simulations. The discussion focuses on how periodic and cluster‐based DFT calculations can provide novel insights into MOF properties, with a focus on predicting structural transformations, understanding thermodynamic properties and catalysis, and providing information or properties that are fed into classical simulations such as force field parameters or partial charges. Classical simulation methods, highlighting force field selection, databases of MOFs for high‐throughput screening, and the synergistic nature of MC and MD simulations, are described. By predicting equilibrium thermodynamic and dynamic properties, these methods offer a wide perspective on MOF behavior and mechanisms. Additionally, the incorporation of machine learning (ML) techniques into quantum and classical simulations is discussed. These methods can enhance accuracy, expedite simulation setup, reduce computational costs, as well as predict key parameters, optimize geometries, and estimate MOF stability. By charting the growth and promise of computational research in the MOF field, the aim is to provide insights and recommendations to facilitate the incorporation of computational modeling more broadly into MOF research.

Alignment of Breathing Metal-Organic Framework Particles for Enhanced Water-Driven Actuation.

As the majority of known metal-organic frameworks (MOFs) possess anisotropic crystal lattices and thus anisotropic physicochemical properties, a pressing practical challenge in MOF research is the establishment of robust and simple processing methods to fully harness the anisotropic properties of the MOFs in various applications. We address this challenge by applying an E-field to precisely align MIL-88A microcrystals and generate MIL-88A@polymer films. Thereafter, we demonstrate the impact of MOF crystal alignment on the actuation properties of the films as a proof of concept. We investigate how different anisotropies of the MIL-88A@polymer films, specifically, crystal anisotropy, particle alignment, and film composition, can lead to the synergetic enhancement of the film actuation upon water exposure. Moreover, we explore how the directionality in application of the external stimuli (dry/humid air stream, water/air interface) affects the direction and the extent of the MIL-88A@polymer film movement. Apart from the superior water-driven actuation properties of the developed films, we demonstrate by dynamometer measurements the higher degree of mechanical work performed by the aligned MIL-88A@polymer films with the preserved anisotropies compared to the unaligned films. The insights provided by this work into anisotropic properties displayed by aligned MIL-88A@polymer films promise to translate crystal performance benefits measured in laboratories into real-world applications. We anticipate that our work is a starting point to utilize the full potential of anisotropic properties of MOFs.

Constructing Physiological Defense Systems against Infectious Disease with Metal-Organic Frameworks: A Review.

The swift and deadly spread of infectious diseases, alongside the rapid advancement of scientific technology in the past several centuries, has led to the invention of various methods for protecting people from infection. In recent years, a class of crystalline porous materials, metal-organic frameworks (MOFs), has shown great potential in constructing defense systems against infectious diseases. This review addresses current approaches to combating infectious diseases through the utilization of MOFs in vaccine development, antiviral and antibacterial treatment, and personal protective equipment (PPE). Along with an updated account of MOFs used for designing defense systems against infectious diseases, directions are also suggested for expanding avenues of current MOF research to develop more effective approaches and tools to prevent the widespread nature of infectious diseases.

Applications of MOFs in Drug Delivery

The main research focus of this article is the application of Metal-Organic Frameworks (MOFs) in drug delivery applications. The review primarily concentrates on the methods used for loading drugs into MOFs, their response to stimuli, potential applications, and limitations. The article begins with discussing the limitations of traditional drug delivery systems and introduces MOFs as a potential solution to these limitations. The drug loading strategy section describes the three main methods for loading drugs into MOFs, including their respective benefits and drawbacks. The stimulus response release program section explores various stimuli that can trigger drug release from MOFs, including physical, chemical, and biological factors, and provides examples of how MOFs can respond to these stimuli. The section on application and challenges provides an overview of current studies exploring the potential of MOFs in biomedical applications, including cancer therapy, antibacterial therapy, and anti-inflammatory therapy, while also highlighting the key challenges facing MOFs research, such as biocompatibility and toxicity. Finally, the article concludes by offering prospects for future developments in MOFs research. This review article provides a significant resource for drug delivery researchers and practitioners who wish to investigating the possibility of utilizing MOFs as novel drug delivery vehicles.

The Upcoming Future of Metal-Organic Frameworks: Challenges and Opportunities

Metal–organic frameworks (MOFs) belong to the group of porous and crystalline substances that enable the diversity of composition and structure beyond conventional solid-state materials. In the past few years’ MOFs have created enormous interest due to their potential applications in clean energy, becoming a storage medium for H2 and CH4. The luminescent metal-organic frameworks (LMOFs) are recognized for a broad range of applications in chemical sensing, energy-efficient lighting, removal of toxic substances from gases and liquids, bio-imaging, and related fields. The present review highlights the basic methods of synthesis, current challenges in the synthesis of novel MOF materials, various characterization methods, scope, and opportunities available for the future related to MOF research. The application of MOF materials in packaging and catalysis was also discussed.Keywords: Luminescent, Metal–organic frameworks (MOFs), Sensors, Storage energies, Supercapacitors.

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers.

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

Review on Metal-Organic Framework Classification, Synthetic Approaches, and Influencing Factors: Applications in Energy, Drug Delivery, and Wastewater Treatment.

Metal ions or clusters that have been bonded with organic linkers to create one- or more-dimensional structures are referred to as metal-organic frameworks (MOFs). Reticular synthesis also forms MOFs with properly designated components that can result in crystals with high porosities and great chemical and thermal stability. Due to the wider surface area, huge pore size, crystalline nature, and tunability, numerous MOFs have been shown to be potential candidates in various fields like gas storage and delivery, energy storage, catalysis, and chemical/biosensing. This study provides a quick overview of the current MOF synthesis techniques in order to familiarize newcomers in the chemical sciences field with the fast-growing MOF research. Beginning with the classification and nomenclature of MOFs, synthesis approaches of MOFs have been demonstrated. We also emphasize the potential applications of MOFs in numerous fields such as gas storage, drug delivery, rechargeable batteries, supercapacitors, and separation membranes. Lastly, the future scope is discussed along with prospective opportunities for the synthesis and application of nano-MOFs, which will help promote their uses in multidisciplinary research.

Metal‐organic framework derived porous structures towards lithium rechargeable batteries

AbstractBatteries are a promising technology in the field of electrical energy storage and have made tremendous strides in recent few decades. In particular, lithium‐ion batteries are leading the smart device era as an essential component of portable electronic devices. From the materials aspect, new and creative solutions are required to resolve the current technical issues on advanced lithium (Li) batteries and improve their safety. Metal‐organic frameworks (MOFs) are considered as tempting candidates to satisfy the requirements of advanced energy storage technologies. In this review, we discuss the characteristics of MOFs for application in different types of Li batteries. A review of these emerging studies in which MOFs have been applied in lithium storage devices can provide an informative blueprint for future MOF research on next‐generation advanced energy storage devices.image

Bio-metal-organic framework-based cobalt glutamate for CO2/N2 separation: Experimental and multi-objective optimization with a neural network

The outstanding properties of metal-organic frameworks (MOFs) have proven that this type of crystalline adsorbent has great potential in CO2 capture applications. Most of the MOF research studies on new functional MOFs are conducted to improve the performance of CO2 gas adsorption. Combined studies of material evaluation and process design on engineering issues in CO2 capture applications in industry are rarely carried out. In this study, the authors attempted to address engineering issues by developing a biometal-organic framework with the bioligand L-glutamic acid that has more practical fabrication cost than petrochemical MOFs. Herein, the demonstration of the prediction and optimization of CO2 adsorption capacity, selectivity, and heat of adsorption using a multiobjective genetic algorithm (MOGA) combined with an artificial neural network (ANN). The success of the Bio-MOF fabrication was evaluated by scanning electron microscopy, N2 adsorption-desorption isotherm analysis, thermal gravimetric analysis, X-ray diffraction, and Fourier transform infrared spectroscopy techniques. Furthermore, volumetric measurements were performed at several temperatures (27, 35 and, 50 °C). The isosteric heat of adsorption was then evaluated by an indirect method with the Clausius-Clapeyron (C-C) and Chakraborty, Saha, and Koyama (CSK) equations. Then, CO2/N2 selectivity was analysed by IAST techniques by regressing the experimental data with the Langmuir-Freundlich isothermal equation. The computational study by ANN and MOGA also gives satisfying results in balancing three requirements criteria. Thus, this study paved the way for the development of low-cost scalable MOF fabrication in industry by applying the optimization and balancing principles of the three objective functions.

Metal‐Organic Frameworks: Synthesis, Structures, and Applications

Metal‐Organic Frameworks: Synthesis, Structures, and Applications

Seed-aided green synthesis of metal-organic frameworks in water

Green synthesis of metal-organic frameworks (MOFs) in water with alleviated environmental influence and reduced cost is an essential step to transfer laboratory MOFs research to industrial application. Switching from the commonly used organic solvents to pure water encounters challenges of the poor solubility of organic linkers, slow reaction kinetics, and the formation of polymorphic products. So far, a universal MOFs synthetic strategy in water system has yet to be developed. This study reports the seed-aided synthesis of eleven MOFs with diverse compositions and structures while pure water serving as solvent. The corresponding reaction temperature and time of using this new strategy were reduced compared with original synthetic approaches, while the products maintain porous structure and high crystallinity. The success of this strategy relies on the addition of parent MOFs as seeds which could promote crystallization process by skipping the time-consuming induction period and avoiding the formation of polymorphic impurities.

Structural Investigation into Magnesium Based MOFs Derived from Aliphatic Linkers

Lightweight metal–organic frameworks (MOFs) with large volume storage capabilities are highly sought after as solid adsorbents in gas storage applications. This is particularly important for hydrogen gas adsorbents and can be explored through constructing MOFs from magnesium, which is a light metal and can readily form lightweight frameworks. Recently, the use of bulky, 3D aliphatic linkers in MOF synthesis has resulted in materials with higher gas adsorption enthalpies at lower pressures. Here, we employ both aliphatic linkers and magnesium clusters to produce lightweight, aliphatic frameworks with potential use for gas adsorption applications. Two magnesium MOFs were synthesised, 3DL-MOF-2 and 3DL-MOF-3 (3DL = 3DLinker), and structurally investigated using single crystal X-ray diffraction. While these MOFs do not have any accessible void spaces and therefore cannot be used for gas adsorption, they create a platform for future magnesium aliphatic MOF research to form open frameworks.