Metal-organic Framework Materials Research Articles

In Situ Electrochemical Reconstruction of Terephthalate Metal–Organic Framework Nanosheets for High‐Efficiency Lithium‐Ion Storage

AbstractThe use of metal–organic frameworks (MOFs) as electrode materials in electrochemical energy storage is still limited to two options, except for a few electrochemically stable MOFs that can be directly used as electrodes. Most of the MOFs often serve as templates for preparing inorganic electrodes. This study demonstrates that terephthalate MOF nanosheet electrodes represent an alternative category for effective electrochemical Li+ storage through an in situ electrochemical reconstruction mechanism. Upon the initial lithiation/de‐lithiation cycles, the original MOF nanosheet assembly transitions to a distinctive plum pudding‐like structure with massive metal oxide nanocrystals embedded in a porous lithium terephthalate matrix, which can deliver a high capacity of 1582.4 mAh g−1 at a current density of 0.1 A g−1 and maintain a reversible capacity of 502.6 mAh g−1 at 2 A g−1 after 2000 cycles. This study offers a valuable reference for designing MOF electrodes and advancing the applications of MOF materials in electrochemistry.

A fluorescent sensor based on pentafluoropropanoic acid-functionalized UiO-66-NH2 for enhanced selectivity and sensitivity of dicloran detection.

Apentafluoropropionic acid-functionalized fluorescent metal-organic framework material (UiO-66-NH2-PFPA) is prepared by a simple post-synthetic modification (PSM) strategy for the sensitive and selective detection of dichloran (DCN). The results of fluorescence experiments demonstrate that the sensitivity of UiO-66-NH2-PFPA (limit of detection, LOD = 0.478μM) to DCN is nearly 10.93 times higher than that of UiO-66-NH2 (LOD = 5.225μM)and the material hasgood selectivity and anti-interference ability. After the addition of DCN, the blue fluorescence of UiO-66-NH2-PFPA is obviously quenched. Therefore, the possible quenching mechanism is further discussed in combination with relevant experiments and density functional theory calculations. Moreover, the sensor is applied to the detection of DCN in fruit samples with a satisfactory recovery of 101.1-107.9%, which implies that UiO-66-NH2-PFPA is expected to be a candidate material for the detection of DCN in food.

Employing Triphenylene-Based, Layered, Conductive Metal-Organic Framework Materials as Electrochemical Sensors for Nitric Oxide in Aqueous Media.

This paper describes the first use of conductive metal-organic frameworks as the active material in the electrochemical detection of nitric oxide in aqueous solution. Four hexahydroxytriphenylene (HHTP)-based MOFs linked with first-row transition metal nodes (M = Co, Ni, Cu, Zn) were compared as thin-film working electrodes for promoting oxidation of NO using voltammetric and amperometric techniques. Cu- and Ni-linked MOF analogs provided signal enhancement of 5- to 7-fold over a control glassy carbon electrode (SANO = 6.7 ± 1.2 and 5.7 ± 1.1 for Ni3(HHTP)2 and Cu3(HHTP)2, respectively) for detecting micromolar concentrations of NO. Zinc-based MOF electrodes offered more limited enhancement (SANO = 3.1 ± 0.5), while the cobalt-based MOF analog had intrinsic redox activity at potentials close to NO oxidation, which interfered with sensing. Combining MOFs with a conductive polymer improved electrode stability under repeated electrochemical scanning (14 ± 3% decrease in signal over 10 scans). The stabilized Ni3(HHTP)2@polymer-coated electrodes were able to detect NO at physiologically relevant concentrations (LOD = 9.0 ± 4.8 nM) in amperometric sensing experiments, and exhibited moderate selectivity against ascorbic acid and nitrite (log kj,NO = -1.3 ± 0.3 and -0.83 ± 0.68 for ascorbic acid and nitrite, respectively). This study demonstrates that layered, conductive 2D MOFs have promising applicability for NO detection in aqueous environments.

Protein-Guided Biomimetic Calcification Constructing 3D Nitrogen-Rich Core-Shell Structures Realizing High-Performance Lithium-Sulfur Batteries.

Biomimetic calcification is a micro-crystallization process that mimics the natural biomineralization process, where biomacromolecules regulate the formation of inorganic minerals. In this study, it is presented that a protein-assisted biomimetic calcification method for the in situ synthesis of nitrogen-doped metal-organic framework (MOF) materials. A series of unique core-shell structures are created by utilizing proteins as templates and guiding agents in the nucleation step, creating ideal conditions for shell growth. To further understand the influence of the protein and organic ligand on the morphology of the MOF shell, the competing mechanism toward metal ions is supposed. Through systematic experiments and analyses, a strategy to construct unique precursor structures by controlling calcification nucleation is proposed. After carbonization, protein-containing precursors exhibit exceptional porous characteristics, stability, and high nitrogen content. These attributes make them promising materials as sulfur hosts in lithium-sulfur batteries (LSB). Electrochemical tests confirm that biomimetic calcification-assisted 3D carbonaceous structure can effectively immobilize dissolved polysulfides, demonstrating strong adsorption and catalytic capabilities. This discovery not only opens up new avenues for employing biomimetic calcification as a sustainable method for batteries but also enlightens the fields of materials science, catalytic chemistry, and energy storage.

Metal-organic frameworks as thermocatalysts for hydrogen peroxide generation and environmental antibacterial applications.

Reactive oxygen species (ROS) are highly reactive, making them useful for environmental and health applications. Traditionally, photocatalysts and piezocatalysts have been used to generate ROS, but their utilization is limited by various environmental and physical constraints. This study introduces metal-organic frameworks (MOFs) as modern thermocatalysts efficiently producing hydrogen peroxide (H2O2) from small temperature differences. Temperature fluctuations, abundant in daily life, offer tremendous potential for practical thermocatalytic applications. As proof of concept, MOF materials coated onto carbon fiber fabric (MOF@CFF) created a thermocatalytic antibacterial filter. The study compared three different MOFs (CuBDC, MOF-303, and ZIF-8) with bismuth telluride (Bi2Te3), a known thermocatalytic material. ZIF-8 demonstrated superior H2O2 generation under low-temperature differences, achieving 96% antibacterial activity through temperature variation cycles. This work advances potential in thermoelectric applications of MOFs, enabling real-time purification and disinfection through H2O2 generation. The findings open interdisciplinary avenues for leveraging thermoelectric effects in catalysis and various technologies.

Design and Construction of a Porphyrin-Based Samarium(III)-Metal-Organic Framework for Antibiotic Detection.

Porphyrins bearing the unique 18π electron tetrapyrrolic macrocycles exhibit interesting photophysical and photochemical properties and have been considered as promising ligands for the construction of functionalized metal-organic frameworks (MOFs). The combination of porphyrin-type ligands with lanthanide metals featured with diverse coordination environments to realize the novel functions as well as the diversity of the MOF is thus attractive but challenging. Herein, an unprecedented porphyrin-based samarium MOF (Sm-BCPP) composed of a 5,10-bis(4-carboxyphenyl)-10,20-diphenyl porphyrin (H2BCPP) ligand and samarium-formed one-dimensional clusters has been constructed via a solvothermal approach, and the synthesized Sm-BCPP has excellent chemical stabilities, exhibiting red luminescence. Interestingly, Sm-BCPP demonstrated excellent fluorescence quenching against commonly used antibiotics, showing an ultrahigh fluorescence quenching constant (KSV) and ultralow detection limit (LOD), among which the detection limit of rifampicin (LOD = 0.33 nM) and nitrofurazone (LOD = 0.24 nM) was found to be lower than most reported MOF materials. Encouragingly, the Sm-BCPP MOF exhibited excellent stability in aqueous solutions at different pH environments, and the detection capability in the natural water environment indicated its practical application potential. The in-depth studies suggested that the mechanism of the fluorescence quenching against antibiotics involved internal filtration effect and photoinduced electron transfer.

Surface Engineering of 2D Metal-Porphyrin Metal-Organic Frameworks Z-Scheme Heterostructure for Boosting and Stable Photocatalytic Hydrogen Evolution.

How to improve the stability and activity of metal-organic frameworks is an attractive but challenging task in energy conversion and pollutant degradation of metal-organic framework materials. In this paper, a facile method is developed by fabricating titanium dioxide nanoparticles (TiO2 NPs) layer on 2D copper tetracarboxylphenyl-metalloporphyrin metal-organic frameworks with zinc ions as the linkers (ZnTCuMT-X, "Zn" represented zinc ions as the linkers, the first "T" represented tetracarboxylphenyl-metalloporphyrin (TCPP), "Cu" represented the Cu2+ coordinated into the porphyrin macrocycle, "M" represented metal-organic frameworks, the second "T" represented TiO2 NPs layer, and "X" represented the added volume of n-tetrabutyl titanate (X = 100, 200, 300 or 400)). It is found that the optimized ZnTCuMT-200 showed greatly and stably enhanced H2 generation, which is ≈28.2 times and 47.0 times as high as those of the original ZnTCuM and TiO2, respectively. Combined with the results of free radical capture, X-ray photoelectron spectra (XPS), electron spin resonance (ESR), and theoretical calculation, a direct Z-scheme electron transfer mechanism is achieved to fully explain the enhanced photocatalytic performance. It demonstrates that facilely designing Z-scheme heterostructures based on porphyrin MOFs modified with an inorganic semiconductor layer can be an advantageous strategy for enhancing the stability and activity of photocatalytic hydrogen evolution.

The Synergistic Effect of MOF and Biomass Achieving Dual Breakthroughs in Material Structure and Performance

In order to cope with the environmental crisis and the depletion of non-renewable resources, the combination of metal-organic framework (MOFs) and biomass materials has become an important breakthrough in sustainable...

Magnetic fluorinated mesoporous metal-organic frameworks for rapid derivatization-assisted GC-MS analysis of perfluoroalkyl carboxylic acids in harsh water environment.

A novel magnetic mesoporous fluorinated metal-organic framework material (Fe3O4@MIP-206-F) has been synthesized specifically for application as an adsorbent for perfluoroalkyl carboxylic acids (PFCAs) extraction by magnetic solid-phase extraction (MSPE). The carefully designed Fe3O4@MIP-206-F material features an appropriate porosity, open metal sites of Zr, and functional groups (fluorine and amino) conducive to the adsorption process. The distinctive architecture of the material endows it with exceptional extraction capabilities for PFCAs. Adsorption mechanisms encompass acid-base interactions, hydrophobic interactions, F-F interactions, electrostatic interactions, and size complementarity. Optimization of key parameters has significantly improved the extraction efficiency of MSPE. When coupled with gas chromatography-mass spectrometry (GC-MS), MSPE offers rapid and highly sensitive analysis of PFCAs. The method demonstrates wide linear range (0.050-50 ng mL-1), low detection limits (0.0010-0.0019 ng mL-1), good recoveries (86.7 % to 111 %), and exceptional intra- and inter-day precision. This approach accurately quantifies PFCAs in lake water and groundwater samples, enabling precise assessment of environmental contamination levels and supporting targeted remediation efforts.

Stability Regulation of Metal-organic Framework Materials for Electrocatalysis

The stability of metal-organic framework materials (MOFs) greatly affects their catalytic performance and cycle life in practical applications. However, while the number and diversity of MOF structures have increased significantly...

Data‐Driven Innovation in Metal‐Organic Frameworks Photocatalysis: Bridging Gaps for CO2 Capture and Conversion with FAIR Principles

Metal‐organic frameworks (MOFs) have emerged as key materials for carbon capture and conversion, particularly in photocatalytic CO2 reduction. However, inconsistent reporting of essential parameters in the literature hinders informed decisions about material selection and optimization. This perspective highlights the need for a user‐friendly, centralized database supported by automated data extraction using natural language processing tools to streamline comparisons of MOF materials. By consolidating crucial data from scientific literature, such a database promotes efficient decision‐making in material selection for CO2 capture and utilization. Emphasizing the significance of open‐source initiatives and the principles of FAIR data—ensuring data are Findable, Accessible, Interoperable, and Reusable—a collaborative approach to data management and sharing is advocated for. Making the database‐accessible worldwide enhances data quality and reliability, fostering innovation and progress in CO2 capture and conversion using MOF materials. Additionally, such databases are valuable in creating artificial intelligence tools to assist researchers in the discovery and synthesis of MOF materials for CO2 capture and conversion.

Boosting Adsorption and Selectivity of Acetylene by Nitro Functionalisation in Copper(II)‐Based Metal–Organic Frameworks

AbstractPurification and storage of acetylene (C2H2) are important to many industrial processes. The exploitation of metal–organic framework (MOF) materials to address the balance between selectivity for C2H2 vs carbon dioxide (CO2) against maximising uptake of C2H2 has attracted much interest. Herein, we report that the synergy between unsaturated Cu(II) sites and functional groups, fluoro (−F), methyl (−CH3), nitro (−NO2) in a series of isostructural MOF materials MFM‐190(R) that show exceptional adsorption and selectivity of C2H2. At 298 K, MFM‐190(NO2) exhibits an C2H2 uptake of 216 cm3 g−1 (320 cm3 g−1 at 273 K) at 1.0 bar and a high selectivity for C2H2/CO2 (up to ~150 for v/v = 2/1) relevant to that in the industrial cracking stream. Dynamic breakthrough studies validate and confirm the excellent separation of C2H2/CO2 by MFM‐190(NO2) under ambient conditions. In situ neutron powder diffraction reveals the cooperative binding, packing and selectivity of C2H2 by unsaturated Cu(II) sites and free −NO2 groups.

A General Nonbonded Force Field Based on Accurate Quantum Mechanics Calculations for Elements H-La and Hf-Rn.

Noncovalent interactions (NCI) play a central role in numerous physical, chemical, and biological phenomena. An accurate description of NCI is the key to success for any theoretical study in such areas. Although quantum mechanics (QM) methods such as dispersion-corrected density functional theory are sufficiently accurate, their applications are practical only for <300 atoms and <100 ps of simulation time. Thus, empirical force fields (FF) have generally been the only choice for systems with thousands to millions of atoms and for nanoseconds and longer. We want to develop a FF that can be applied to applications of thousands to millions of atoms with an accuracy comparable to QM methods. As the first step, we develop here a new general nonbonded potential (GNB) based on a novel functional form with four adjustable parameters for each element. We report here parameters for elements H-La, Hf-Rn (excluding lanthanides and actinides) by fitting the interaction energy of molecular complexes to QM calculations using the accurate Head-Gordon ωB97M-V density functional. We performed extensive testing of GNB for organic molecules, organometallic molecules, and metal organic-framework (MOF) systems. The mean absolute errors of GNB are 0.37 kcal/mol for the dispersion and mixed groups of the S66 × 8 benchmark set, 0.35 kcal/mol for CO2 adsorption on MOF materials, and 4.53 kcal/mol for the XTMC43 benchmark. GNB outperforms existing FF and in many cases has accuracy comparable to that of QM methods such as PBE-D3. GNB can potentially replace the nonbonded part of existing FFs in a wide range of applications.

Electrochemical Synthesis and Conductivity Fine Tuning of the 2D Iron-Quinoid Metal-Organic Framework.

Electrically conducting 2D metal-organic frameworks (MOFs) with hexagonal 2D lattices like other 2D van der Waals stacked materials are attracting increasing interest. The conductivity can be effectively regulated through electronic structure adjustment thanks to the chemical and physical flexibility and adjustability of MOFs. In this regard, through a simple and rapid electrochemical method, 2D conductive iron-quinoid MOFs were synthesized. The conductivity of the obtained MOF film reached 1.7(7) S/m. With the increase of reaction time, the 2D network was oxidized partially, and the conductivity decreased down to 0.5(7) S/m. The DFT calculation results showed a narrow bandgap of the 2D crystal cell. Further quantum chemical calculations of the bimetal unit of the iron-quinoid MOF revealed the expansion of the bandgap as the 2D MOF network is gradually oxidized. This work proves the feasibility of fine-tuning macroscopic conductivity from an electronic structure. The combined organic and inorganic chemical structure of MOF materials provides a larger operating space for this fine regulation than that of pure inorganic materials. This conductive 2D iron-quinoid MOF film provides a new option for the development of novel microelectronic devices.

Efficient Adsorption of Ionic Liquids in Water Using -SO3H-Functionalized MIL-101(Cr): Adsorption Behavior and Mechanism.

With the increasing application of ionic liquids (ILs) in industrial areas, the removal of ILs from aqueous media has attracted considerable attention due to their potential environmental impact. In this study, we investigated the adsorption behavior and removal mechanism of ILs in water using the metal-organic framework material MIL-101(Cr) and its sulfonated derivative MIL-101(Cr)-SO3H. It was observed that MIL-101(Cr)-SO3H exhibited notably elevated adsorption capacity (1.19 mmol/g) and rapid adsorption kinetics (1.66 g/mmol·min-1) for [C4mim]Cl in comparison to its unmodified form, underscoring the impact of strategic sulfonation on enhancing adsorption. Also, MIL-101(Cr)-SO3H showcased the effective removal of various ILs featuring diverse cations and varying anions, highlighting its broad-spectrum capture capacities. The adsorption process is less influenced by the type of cations and anions. In contrast, enhanced adsorption of [C16mim]Cl by MIL-101(Cr)-SO3H demonstrated that the length of the alkyl chain of ILs' cation exerted a more significant influence on the adsorption than the type of head and tail group. This enhancement is attributed to a synergistic interplay of pore filling, electrostatic interactions, hydrophobic interactions, and micelle enrichment. These findings provided valuable insights into optimizing the design of metal-organic framework materials for the efficient removal of IL pollutants.

Research Progress on the Application of MOF Materials in Lithium‐Ion Batteries

ABSTRACTLithium‐ion batteries (LIBs) have established themselves as the preferred power sources for both pure electric and hybrid vehicles, attributable to their exceptional characteristics, including prolonged cycle life, elevated energy density, and minimal self‐discharge rates. Metal‐organic frameworks (MOFs), as innovative functional molecular crystal materials, exhibit promising application prospects in LIBs. This paper provides a comprehensive overview of the latest advancements in the synthesis techniques and structural modulation of MOFs and their derivative materials. It particularly emphasizes a thorough exploration of the utilization of MOFs and their derivatives in the anode, cathode, and separators of LIBs. Additionally, this paper delves into the current obstacles encountered by MOFs in LIB applications and offers insights into their potential future development.

Hybrid Metal-Organic Frameworks (MOFs) for Various Catalysis Applications.

Porous materials have been gaining popularity in catalysis applications, solving the current ecological challenges. Metal-organic frameworks (MOFs) are especially noteworthy for their high surface areas and customizable chemistry, giving them a wide range of potential applications in catalysis remediation. The review study delves into the various applications of MOFs in catalysis and provides a comprehensive summary. This review thoroughly explores MOF materials, specifically focusing on their diverse catalytic applications, including Lewis catalysis, oxidation, reduction, photocatalysis, and electrocatalysis. Also, this study emphasizes the significance of high-performance MOF materials, which possess adjustable properties and exceptional features, as a novel approach to tackling technological challenges across multiple sectors. MOFs make it an ideal candidate for catalytic reactions, as it enables efficient conversion rates and selectivity. Furthermore, the tunable properties of MOF make it possible to tailor its structure to suit specific catalytic requirements. This feature improves performance and reduces costs associated with traditional catalysts. In conclusion, MOF materials have revolutionized the field of catalysis and offer immense potential in solving various technological challenges across different industries.

Surface Engineering of 2D Metal-Porphyrin Metal-Organic Frameworks Z-Scheme Heterostructure for Boosting and Stable Photocatalytic Hydrogen Evolution.

How to improve the stability and activity of metal-organic frameworks is an attractive but challenging task in energy conversion and pollutant degradation of metal-organic frameworks materials. In this paper, we developed a facile method by fabricating TiO2 nanoparticles (NPs) layer on 2D copper tetracarboxylphenyl-metalloporphyrin metal-organic frameworks (MOFs) with Zn2+ as the linkers (ZnTCuMT-X, "Zn" represented Zn2+ as the linkers, the first "T" represented tetracarboxylphenyl-metalloporphyrin (TCPP), "Cu" represented the Cu2+ coordinated into the porphyrin macrocycle, "M" represented MOFs, the second "T" represented TiO2 NPs layer, and "X" represented the added volume of n-tetrabutyl titanate (X = 100, 200, 300 or 400)). It was found that the optimized ZnTCuMT-200 showed greatly and stably enhanced H2 generation, which was about 28.2 times and 47.0 times as high as those of the original metalloporphyrin MOFs and TiO2, respectively. Combined with the results of free radical capture, X-ray photoelectron spectra, electron spin resonance and theoretical calculation, a direct Z-scheme electron transfer mechanism was achieved to fully explain the enhanced photocatalytic performance. It demonstrates that facilely designing Z-scheme heterostructures based on porphyrin MOFs modified with inorganic semiconductor layer could be an advantageous strategy for enhancing the stability and activity of photocatalytic hydrogen evolution.

Ultrafast synthesis and binder‐free fabrication of a monolithic metal–organic framework for efficient carbon capture

AbstractAchieving rapid synthesis alongside efficient shaping without sacrificing high porosity and crystallinity poses significant challenges for metal–organic frameworks (MOFs) in practical applications. Here, we report an ultrafast, scalable method for preparing an ultramicroporous MOF at room temperature. This method achieves a space–time yield significantly higher than conventional MOF synthesis by orders of magnitude. As a result of strongly promoted crystal nucleation by careful selection of solvent and metal source, the MOF material is produced in a gel state offering both high crystallinity and processability. This allows for the binder‐free fabrication of monolithic adsorbents with predesigned macro shapes and sizes. Owing to its narrowly distributed pore size and high‐density open metal sites, the monolithic adsorbent demonstrates top‐tier selectivity for CO2/N2 (&gt;200) and CO2/CH4 separations. The performance sets a new benchmark among current MOF xero‐ or aerogel monoliths. Breakthrough experiments further verify its robust ability for carbon capture under dynamic conditions.

Metal‐Organic Frameworks for Advanced Electrochemical Ammonia Production in Water

AbstractSustainable ammonia synthesis, a key focus in electrochemistry, has seen significant advancements with the emergence of Metal‐Organic Frameworks (MOFs). This review provides a comprehensive analysis of the recent strides in MOF‐based materials for green ammonia production, reflecting the urgency to develop eco‐friendly and energy‐efficient chemical commodities. It explores the reaction mechanisms, emphasizing the importance of structure‐performance relationships in MOF optimization and the design of MOF‐based electrocatalysts, including metal node engineering and hybrid materials. The review also highlights in‐situ characterization techniques that are crucial for understanding MOF catalytic activity. It establishes a correlation between MOF features, synthesis methods, and material performance, showcasing their potential in catalysis. Finally, it identifies challenges and future directions for MOFs in green ammonia production, aiming to inspire innovation towards sustainable and economically viable processes.