Metal-organic Frameworks Nanostructures Research Articles

Electrodeposited nickel-manganese terephthalic acid metal organic framework for hybrid battery and water splitting

Metal-organic frameworks (MOFs) possessing great potential towards energy storage and conversion applications has led to the intensive investigation of these materials. MOFs are distinguished by their remarkable properties such as customizable pore topologies and abundant redox-active sites. The present investigation showcases the electro-synthesis of flake-like bimetallic nickel-manganese-Terephthalic acid (NiMn-T) MOF nanostructures on nickel foam, an inventive electrode material, in the absence of a binder. Emphasis has been made on the significance of controlling time of electrodeposition to achieve optimum electrochemical performance. The best performing NiMn-T MOF electrode exhibits notable electrochemical characteristics, and therefore integrated as a hybrid supercapacitor’s electrode. The fabricated hybrid device delivers decent energy and power density. From the perspective of water splitting characterizations, NiMn-T MOF showed good HER and excellent OER activities along with an exceptional OER stability of 103 % over 10 h demonstrating its capability for its incorporation into practical applications. Hence, this strategy offers a direct and innovative strategy for the advancement of binder-free electrodes in preparation for the energy storage and conversion systems of the next generation.

Metal-Organic Framework-Based Nanostructures for Electrochemical Sensing of Sweat Biomarkers.

Sweat is considered the most promising candidate to replace conventional blood samples for noninvasive sensing. There are many tools and optical and electrochemical methods that can be used for detecting sweat biomarkers. Electrochemical methods are known for their simplicity and cost-effectiveness. However, they need to be optimized in terms of selectivity and catalytic activity. Therefore, electrode modifiers such as nanostructures and metal-organic frameworks (MOFs) or combinations of them were examined for boosting the performance of the electrochemical sensors. The MOF structures can be prepared by hydrothermal/solvothermal, sonochemical, microwave synthesis, mechanochemical, and electrochemical methods. Additionally, MOF nanostructures can be prepared by controlling the synthesis conditions or mixing bulk MOFs with nanoparticles (NPs). In this review, we spotlight the previously examined MOF-based nanostructures as well as promising ones for the electrochemical determination of sweat biomarkers. The presence of NPs strongly improves the electrical conductivity of MOF structures, which are known for their poor conductivity. Specifically, Cu-MOF and Co-MOF nanostructures were used for detecting sweat biomarkers with the lowest detection limits. Different electrochemical methods, such as amperometric, voltammetric, and photoelectrochemical, were used for monitoring the signal of sweat biomarkers. Overall, these materials are brilliant electrode modifiers for the determination of sweat biomarkers.

Highly Performing Sodium Metal Batteries Reinforced by a Self-Regulated Dual-Layered Solid Electrolyte Interphase via a Metal-Organic Framework.

Sodium-metal batteries, heralded for high energy density and cost-effectiveness, are compromised by an unstable solid electrolyte interphase (SEI) and dendrite formation, which hinder practical applications. Herein, a zirconium-based metal-organic framework nanostructure coating (ZMOF-NSC) was constructed in a low-loss, flexible manner. Comprehensive studies show that ZMOF-NSC, with its periodically ordered nanochannels and organized pore structures, enhances ion transport and decreases the Na+ migration energy barrier, thus ensuring uniform ion flux and achieving uniform spherical deposition. Additionally, ZMOF-NSC facilitates partial desolvation, catalyzing the formation of an inorganic-rich, dual-layered SEI that effectively protects the anode and suppresses dendrite formation. Consequently, the ZMOF-NSC@Na symmetric battery exhibits an impressive lifespan of over 2500 h, demonstrating extended operational longevity. The Na3V2(PO4)3∥ZMOF-NSC@Na batteries demonstrate exceptional cycling stability with 81% capacity retention after 2000 cycles at 10 C, maintaining stability over 3000 cycles at 20 C. Moreover, the NVP∥ZMOF-NSC@Na battery achieves an energy density of 370 Wh kg-1 and a power density of 10,484 W kg-1, indicating superior durability and performance. This significant finding highlights the significant potential of structured MOFs to induce a dual-layered SEI, advancing the commercialization of durable, dendrite-free sodium metal batteries. The precise design of self-assembled pore structures and surface active sites in MOFs demonstrates significant potential in advancing the commercialization of durable, dendrite-free electrodes of metal-based rechargeable batteries.

Unveiling the mechanisms behind high CO2 adsorption by the selection of suitable ionic liquids incorporated into a ZIF-8 metal organic framework: A computational approach

There is growing focus on the crucial task of effectively capturing carbon dioxide (CO2) from the atmosphere to mitigate environmental consequences. Metal-organic frameworks (MOFs) have been used to replace many conventional materials in gas separation, and the incorporation of ionic liquids (ILs) into porous MOFs has shown promise as a new technique for improving CO2 capture and separation. However, the driving force underlying the electronic modulation of MOF nanostructures and the mechanisms behind their high CO2 adsorption remain unclear. This study reports the effect of encapsulating different imidazolium ILs in porous ZIF-8, to clarify the adsorption mechanism of CO2 using density functional theory (DFT)-based approaches. For this purpose, a range of anions, including bis(trifluoromethylsulfonyl)imide [NTf2], methanesulfonate [MeSO3], and acetate [AC], were combined with the 1-ethyl-3-methylimidazolium [EMIM]+ cation. [EMIM]+-based ILs@ZIF-8 composites were computationally investigated to identify suitable materials for CO2 capture. First, the intermolecular and intramolecular interactions between [EMIM]+ and different anions were examined in detail, and their effects on CO2 adsorption were explored. Subsequently, the integration of these ILs into the ZIF-8 solid structure was studied to reveal how their interactions influenced the CO2 adsorption behavior. Our results demonstrate that the incorporation of ILs strongly affects the adsorption capability of CO2, which is highly dependent on the nature of the ILs inside the ZIF-8 framework. DFT simulations further confirmed that the incorporation of ILs into ZIF-8 led to superior CO2 capture compared to isolated ILs and pristine ZIF-8. This improvement was attributed to the mutual interactions between the ILs and ZIF-8, which effectively fine-tuned CO2 adsorption within the composite structure. This understanding may act as a general guide for gaining more insight into the interfacial interactions between ILs and ZIFs structures and how these molecular-level interactions can help predict the selection of ILs for CO2 adsorption and separation, thereby addressing environmental challenges with greater precision and effectiveness.

Binder-Free Defective Bimetallic Metal-Organic Framework Nanostructures with Lattice Distortion as Hybrid Supercapacitor Electrodes

Binder-Free Defective Bimetallic Metal-Organic Framework Nanostructures with Lattice Distortion as Hybrid Supercapacitor Electrodes

Synthesis and characterization of safranal@MIL-88B(Fe) nanostructures and their preliminary anticancer and antibacterial characteristics

Fe-based metal-organic framework nanostructures loaded with Safranal show potential as anticancer and antibacterial formulations.

Pioneering ultra-efficient oxygen evolution reaction: A breakthrough in tri-metallic organic frameworks synthesis

The remarkable potential of metal-organic frameworks (MOFs) has garnered significant attention, primarily attributed to their unique and adjustable structural characteristics, which hold promise for various applications, including electrocatalysis. Nevertheless, utilizing MOFs directly in oxygen electrocatalysis presents a formidable challenge due to the intricate control needed to modulate their size, composition, and morphology while ensuring an abundance of active sites. Here, we present a straightforward synthesis method that generates novel NiCoFe-based trimetallic MOF nanostructures. These structures demonstrate exceptional catalytic performance in the oxygen evolution reaction (OER) under alkaline conditions when employed as catalysts. Specifically, the FeNi2Co1-MOF exhibits the crucial overpotential of 143 mV required to attain a current density of 10 mA cm−2. Furthermore, it showcases a low Tafel slope of 68 mV dec−1 and maintains outstanding durability throughout extensive long-term testing.

Post-Synthetic Generation of Amino-Acid-Functionalized UiO-66-NH2 Metal–Organic Framework Nanostructures as an Amphoteric Catalyst for Organic Reactions

Post-Synthetic Generation of Amino-Acid-Functionalized UiO-66-NH₂ Metal–Organic Framework Nanostructures as an Amphoteric Catalyst for Organic Reactions

Facile synthesis of nanostructured sodium and MoS2 incorporated Ni-MOFs with excellent cyclic durability for symmetric supercapacitor application

Highly porous and nanostructured metal-organic frameworks (MOFs) have fascinated enormous interest as electrode active materials for electrochemical energy storage systems, whereas their practical applications are significantly hindered by their relative inferior energy density and cyclability. In this study, MoS2 with layered structure was successfully incorporated onto hierarchical Ni-MOFs via a facile hydrothermal approach. Moreover, sodium cations were introduced to improve electronic conductivity. The resulting nanocomposites (sodium ions and MoS2 incorporated Ni-MOFs) exhibited hierarchical porous structures with varying dimensions, offering increased volume for charge storage and diffusion channels for electrolyte ions. Benefiting from the unique topological architectures, the as-synthesized porous nanocomposites delivered an excellent supercapacitive performance, achieving a superlative energy of 33.33 Wh kg−1 and a power density of 3390 W kg−1. Furthermore, the as-fabricated symmetric supercapacitor device delivered a remarkable cycling durability where the acquired outstanding capacitance retention was 97.42% and coulombic efficiency was 97.82% respectively over more than 10,000 cycles in an aqueous electrolyte.

Highly sensitive self-powered piezoelectric poly(vinylidene fluoride)-based nanofibrous mat containing microporous metal–organic framework nanostructures for energy harvesting applications

Highly sensitive self-powered piezoelectric poly(vinylidene fluoride)-based nanofibrous mat containing microporous metal–organic framework nanostructures for energy harvesting applications

A Microporous Ni(II) Metal–Organic Framework Nanostructure with an Aspartate-Derived Tricarboxylate for Gas/Vapor Sorption and Size-Selective CO2 Chemical Fixation under Solvent-Free Conditions

A Microporous Ni(II) Metal–Organic Framework Nanostructure with an Aspartate-Derived Tricarboxylate for Gas/Vapor Sorption and Size-Selective CO₂ Chemical Fixation under Solvent-Free Conditions

Cooperative Heterogeneous Catalysis with a Robust Acid–Base Bifunctional Zinc-Based Metal–Organic Framework Nanostructure in the Diastereoselective Henry Reaction

Cooperative Heterogeneous Catalysis with a Robust Acid–Base Bifunctional Zinc-Based Metal–Organic Framework Nanostructure in the Diastereoselective Henry Reaction

Cerium(IV)-Based Metal–Organic Framework Nanostructures Grown on 3D-Printed Free-Standing Membranes and Their Derivatives for Charge Storage

Cerium(IV)-Based Metal–Organic Framework Nanostructures Grown on 3D-Printed Free-Standing Membranes and Their Derivatives for Charge Storage

Insight into the Structure of MOF-Containing Hybrid Polymeric Microspheres.

Polymer science exploited metal organic frameworks (MOFs) for various purposes, which is due to the fact that these materials are ideal platforms for identifying design features for advanced functional materials. The mechanism of polymerization using MOFs, is still largely unexplored and the detailed characterization of both materials in essential to understand the important interactions between the components. In this work modern advanced research methods were used to investigate the properties of MOF-containing hybrid polymeric microspheres. Hydrothermal conversion of CFA-derived iron particles was used to obtain MOF nanostructures, which were then introduced to the structure of hybrid polymer microspheres based on ethylene glycol dimethylacrylate (EGDMA) and triethoxyvinylsilane (TEVS). Chemical structures were confirmed by ATR-FTIR method. To provide information about the elemental composition of the tested materials and for the determination of chemical bonds present in the tested samples XPS method was applied. Morphology was studied using SEM microscopy, whereas porosity was investigated using ASAP technique. Swellability coefficients were determined using typical organic solvents and distilled water. Moreover, the ecological aspect concerning the use of fly ashes deserves to be emphasized.

Synthesis of Cu/Co-hybrid MOF as a multifunctional porous compound in catalytic applications, synthesis of new nanofibers, and antimicrobial and cytotoxicity agents

Several biological properties of metal–organic frameworks (MOFs) and fiber compounds have been reported, and combinations of these structures can have unique properties. In this study, copper-containing and cobalt-containing MOF nanostructures were synthesized by the ultrasonic technique. Then, novel Cu/Co-hybrid MOF nanostructures were synthesized using the ultrasonic method. Synthesized Cu/Co-hybrid MOF nanostructures were used as a new and efficient recyclable catalyst in the synthesis of pyrano[2,3-c]pyrazole derivatives using the four-component reaction of phenylhydrazine, ethyl acetoacetate, malononitrile, and aldehyde. In the following, novel Cu/Co-hybrid MOF/PVA (poly vinyl alcohol) fiber nanostructures were synthesized by electrospinning and using Cu/Co-hybrid MOF nanostructures and PVA. The structures of the Cu/Co-hybrid MOF nanostructures and the Cu/Co-hybrid MOF/PVA fiber nanostructures were identified and confirmed using BET, TGA, FTIR, SEM, and XRD. In biological studies, the antibacterial, antifungal, and cytotoxicity activities of Cu/Co-hybrid MOF and Cu/Co-hybrid MOF/PVA fiber nanostructures were evaluated. In investigating the catalytic activity of Cu/Co-hybrid MOF, pyrano[2,3-c]pyrazole derivatives were synthesized with higher efficiency and less time than previously reported methods. High antibacterial (against gram-negative and gram-positive strains) and antifungal properties of synthesized Cu/Co-hybrid MOF nanostructures and Cu/Co-hybrid MOF/PVA fiber nanostructures were observed (MIC between 16 and 256 μg/mL), which were higher than some commercial drugs. In the investigation of cytotoxicity activity, the effectiveness on breast cancer cells was studied. The maximum cell proliferation and viability for Cu/Co-hybrid MOF and Cu/Co-hybrid MOF/PVA fiber nanostructures were 38% and 38% higher than the control in a concentration of 200 μg/mL after 48 h. The high catalytic and biological properties of the synthesized nanoparticles can be attributed to the presence of nano-sized bioactive metals and their high specific surface area. The significant physical-chemical properties obtained for synthesized nanoparticles in this study can be related to the desirable synthesis methods, the development of materials with high purity, and the incorporation of hybrid compounds into the nanostructures.

TMU-16-NH2: A Metal–Organic Framework as an Efficient, Green, and Heterogeneous Catalyst for the Michael Addition Annulations for the Synthesis of a New Series of 2,4-Diphenylpyrido[4,3-d]Pyrimidines

ABASTRACT Considering the unprecedented attributes governed by metal-organic framework nanostructures, the present report discloses the fabrication of [Zn2(H2N-BDC)2(4-bpdh)]·3DMF as a Zn-based MOF catalyst (TMU-16-NH2 (TMU = Tarbiat Modares University)) through the coordination of 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh) ligand to the Zn(NO3)2·6H2O salt under hydrothermal approach. In order to certify the successful synthesis of the catalyst, FT-IR, XRD, TGA, Elemental microanalysis, ICP OES and BET measurements were employed. The developed TMU-16-NH2 catalytic agent acts as a promising candidate to deliver a new class of pharmaceutically relevant 2,4-diphenylpyrido[4,3-d]pyrimidine scaffolds via the Michael addition annulations of benzimidamid hydrochloride to (3E,5E)-3,5-bis-(benzylidene)-4-piperidone reacting species. The devised methodology is accompanied with noteworthy benefits including mild reaction conditions, wide substrate scope, excellent product yields and short reaction span. Besides, facile retrievability and remarkable reusability of the catalyst for 5 successive runs without any appreciable loss in catalytic efficacy are the additional factors that rationalize this protocol as worthwhile. Our findings highlight the potential of using MOFs as efficient and versatile catalysts in organic synthesis and contribute to the growing body of literature on the synthesis of pyrido[4,3-d]pyrimidines with diverse biological activities.

Construction of Three-Dimensional Dendritic Hierarchically Porous Metal-Organic Framework Nanoarchitectures via Noncentrosymmetric Pore-Induced Anisotropic Assembly.

As a unique class of modular nanomaterials, metal-organic framework (MOF) nanoparticles have attracted widespread interest for use in various fields because of their diverse chemical functionalities, intrinsic microporosity, and three-dimensional (3D) nanoarchitectures. However, endowing MOF nanomaterials with precisely controlled structural symmetries and hierarchical macro/mesoporosities remains a formidable challenge for the researchers. Herein, we report a facile noncentrosymmetric pore-induced anisotropic assembly strategy to prepare a series of 3D dendritic MOF (UiO-66) nanomaterials with highly controllable structural symmetries and hierarchical macro/meso/microporosities. The synthetic route of these nanomaterials depends on the anisotropic nucleation of MOF spherical nanocones with noncentrosymmetric center-radial channels and their oriented growth to isotropic nanospheres through a continuous increase in radius and solid angle. This strategy enables the controllable fabrication of asymmetric MOF nanostructures with abundant geometries and porous structures by regulating the concentration of amphiphilic triblock copolymer templates. Furthermore, the average pore diameter of the resultant MOF nanospheres can be systematically manipulated in a wide range from 35 to 130 nm by finely tuning the reaction temperature. Meanwhile, the strategy can also be extended to synthesize other MOF nanoparticles with similar architectures. Compared with microporous UiO-66 nanocrystals, the MOF nanoparticles with controllable structural symmetries and macro/meso/microporosities show enhanced catalytic activity in the CO2 cycloaddition reaction. The methodology provides new insights into the rational construction of sophisticated asymmetric open nanostructures of hierarchically porous MOFs for many potential applications.

Nanoarchitectonics of Bimetallic MOF@Lab-Grade Flexible Filter Papers: An Approach Towards Real-Time Water Decontamination and Circular Economy.

This study presents a novel approach to decontaminate ferrocyanide-contaminated wastewater. The work effectively demonstrates the use of bimetallic Mo/Zr-UiO-66 as a super-adsorbent for rapid sequestration of Prussian blue, a frequently found iron complex in cyanide-contaminated soils/groundwater. The exceptional performance of Mo/Zr-UiO-66 is attributed to the insertion of secondary metallic sites, which deliver synergistic effects, benefiting the inherent qualities of the framework. Moreover, to extend the industrial applications of metal-organic frameworks (MOFs) in real-world scenarios, an approach is delivered to structure the nanocrystalline powders into MOF-based macrostructures. The work demonstrates an interfacial process to develop continuous MOF nanostructures on ordinary laboratory-grade filter papers. The novelty of the work lies in the development of robust free-standing filtration materials to purify PB dye-contaminated water. Additionally, the work embraces a circular economy concept to address problems related to resource scarcity, excessive waste production, and maintenance of economic benefits. Consequently, the PB dye-loaded adsorbent waste is re-employed for the adsorption of heavy metals (Pb2+ and Cd2+ ). Simultaneously, the study aims to address the problems related to the real-time handling of powdered adsorbents, and the generation of ecologically harmful secondary waste, thereby, progressing toward a more sustainable system.

Simultaneous Defect and Size Control of Metal–Organic Framework Nanostructures for Highly Efficient Carbon Dioxide Electroreduction to Multicarbon Products

Simultaneous Defect and Size Control of Metal–Organic Framework Nanostructures for Highly Efficient Carbon Dioxide Electroreduction to Multicarbon Products

Optimization Strategies of the Design and Preparation of Metal–Organic Framework Nanostructures for Water Sorption: A Review

Optimization Strategies of the Design and Preparation of Metal–Organic Framework Nanostructures for Water Sorption: A Review