Fabrication Of Metal-organic Frameworks Research Articles

Metal-organic framework membranes with scale-like structure for efficient propylene/propane separation

The fabrication of metal-organic framework (MOF) membranes with high propylene/propane selectivity, high mechanical endurance and ease of scaling up always remains a challenge. Inspired by the ubiquitous biological wear-resistant structure, here we show ZIF-67 membranes with a tangential-normal interlaced structure (TN-ZIF-67) for one-step acquisition of polymer-grade propylene, which is endowed with the merits of intergranular defect elimination, partial ZIF-67 lattice flexibility restriction and anti-wear of the membrane surface. The TN-ZIF-67 membrane exhibits an optimal propylene/propane mixture separation factor of 221, and the separation performance remained unchanged after 1.5 years of storage or abrasion by repeated sanding. The distinctive membrane structure can be further scaled up on 4 mm-diameter tubular substrates. This work demonstrates a strategy to extend the rational design of defect-free, anti-wear MOF membranes with superior separation performance and stability that could fulfill future industrial applications.

Rational MOF Membrane Design for Gas Detection in Complex Environments.

Metal-organic frameworks (MOFs) hold significant promise in the realm of gas sensing. However, current understanding of their sensing mechanisms remains limited. Furthermore, the large-scale fabrication of MOFs is hampered by their inadequate mechanical properties. These two challenges contribute to the sluggish development of MOF-based gas-sensing materials. In this review, the selection of metal ions and organic ligands for designing MOFs is first presented, deepening the understanding of the interactions between different metal ions/organic ligands and target gases. Subsequently, the typical interfacial synthesis strategies (gas-solid, gas-liquid, solid-liquid interfaces) are provided, highlighting the potential for constructing MOF membranes on superhydrophobic and/or superhydrophilic substrates. Then, a multi-scale structure design strategies is proposed, including multi-dimensional membrane design and heterogeneous membrane design, to improve sensing performance through enhanced interfacial mass transfer and specific gas sieving. This strategy is anticipated to augment the task-specific capabilities of MOF-based materials in complex environments. Finally, several key future research directions are outlined with the aim not only to further investigate the underlying sensing principles of MOF membranes but also to achieve efficient detection of target gases amidst interfering gases and elevated moisture levels.

Fine-Scale Aerosol-Jet Printing of Luminescent Metal-Organic Framework Nanosheets.

Fabrication of metal-organic framework (MOF) thin films is an ongoing challenge to achieve effective device integration. Inkjet printing has been employed to print various luminescent metal-organic framework (MOF) films. Luminescent metal-organic nanosheets (LMONs), nanometer-thin particles of MOF materials with comparatively large micrometer lateral dimensions, provide an ideal morphology that offers enhancements over analogous MOFs in luminescent properties such as intensity and photoluminescent quantum yield. The morphology is also better suited to the formation of thin films. This work harnesses the preferential features of LMONs to access the advanced technique of aerosol-jet printing (AJP) to print luminescent films with precise geometries and patterns across the micrometer and centimeter length scales. AJP of LMONs exhibiting red (R), green (G), and blue (B) emission were studied systematically to reveal the increase of luminescence upon additive layering printing until a threshold was reached limited by self-quenching. By combining different LMON emitters, emission chromaticity and intensity were shown to be tunable, including the combination of RGB emitters to fabricate white-light-emitting films. A white-light LMON film was printed onto a UV light emitting diode (LED), producing a working white-light-emitting diode. Printing with multiple distinct photoluminescent inks produced intricate multicolor patterns that dynamically responded to excitation wavelength, acting either as micrometer-scale LED-type cells or larger visual tags. Collectively, the work offers an advancement for MOF thin films by printing MON materials using AJP, offering a precise method for manufacturing a wide range of critical functional devices, from luminescent sensors to optoelectronics, and more broadly even the opportunity for printed circuitry with conductive MONs.

Fabrication of metal-organic frameworks containing Cu2+ coated medical PVC catheters with durable antiplatelet and antibacterial activities

Polyvinyl chloride (PVC) catheters are widely used in medical environments especially in blood-contacting devices. In this study, a copper containing MOF material was coated on a PVC catheter to endow it with antiplatelet adhesion and antibacterial activity for potential clinical applications. The immobilization of the coordination polymer containing Cu2+ (Cu-MOF) on the inner surface of PVC catheters was carried out using a bioinspired coating combined with a layer-by-layer self-assembly strategy. Characterization of the Cu-MOF modified surfaces was confirmed using micro-infrared spectroscopy (MIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and water contact angle measurements (WCA). The resultant modified surfaces significantly reduced non-specific adsorption to model proteins with excellent anti-biofouling activity, as well as significantly inhibited the platelet adhesion and activation with superior antiplatelet activity. In vitro whole blood circulation test using a peristaltic pump also showed good antithrombotic properties. Besides, the Cu-MOF modified surfaces exhibited good hemocompatibility (hemolysis ratio < 5 %) and excellent antibacterial activity (approximately 97 % against S. auerus and E. coli). This study develops a simple and effective method for the surface modification of medical PVC catheter as potential blood-contacting biomaterials.

An enhanced field emission for display devices arises from the assembling of ZnO@MOF/MWCNTs

In this study, we propose a new, simple technique for raising the efficiency of field emission devices based on metal organic framework composites. Multi-walled carbon nanotubes (MWCNTs) and ZnO are used in the fabrication of metal-organicframeworks (MOFs) in this technique. This is explained by the composites unique structural structure, which offers a lot of easily available electro active sites, low surface work function, and improved electronic conductivity. One of the less complicated and more economical synthesis methods is used to synthesize the ZnO@MOF/MWCNTs composite. The material's precise morphological and structural features have all been investigated using Raman, FE-SEM, EDX, FTIR, and UV–Visible investigations. The ZnO@MOF/MWCNTs field emitter show impressive and stable field emission properties, such as a low turn-on electric field 0.50 V/μm and a high emission current density 219.15 mA/cm2.Our research revealed an easier way for boosting the electron field emission utilized in different field emission display systems that are based on MOFcomposites.

Recent progress and perspectives of metal organic frameworks (MOFs) for the detection of food contaminants

Over the past decades, increasing research in metal-organic frameworks (MOFs) being a large family of highly tunable porous materials with intrinsic physical properties, show propitious results for a wide range of applications in adsorption, separation, electrocatalysis, and electrochemical sensors. MOFs have received substantial attention in electrochemical sensors owing to their large surface area, active metal sites, high chemical and thermal stability, and tunable structure with adjustable pore diameters. Benefiting from the superior properties, MOFs and MOF-derived carbon materials act as promising electrode material for the detection of food contaminants. Although several reviews have been reported based on MOF and its nanocomposites for the detection of food contaminants using various analytical methods such as spectrometric, chromatographic, and capillary electrophoresis. But there no significant review has been devoted to MOF/and its derived carbon-based electrodes using electrochemical detection of food contaminants. Here we review and classify MOF-based electrodes over the period between 2017 and 2022, concerning synthetic procedures, electrode fabrication process, and the possible mechanism for detection of the food contaminants which include: heavy metals, antibiotics, mycotoxins, and pesticide residues. The merits and demerits of MOF as electrode material and the need for the fabrication of MOF and its composites/derivatives for the determination of food contaminants are discussed in detail. At last, the current opportunities, key challenges, and prospects in MOF for the development of smart sensing devices for future research in this field are envisioned.

Fabrication of metal-organic frameworks with trimesic linkers for europium adsorption and recovery from aqueous solutions

This work reports on the effective sequestration of Eu(III) ions from aqueous solutions using three types of metal-organic frameworks (MOFs) constructed from benzene-1,3,5-tricarboxylic acid (H3BTC) linker and Ca2+, Cu2+, or Al3+ metal nodes. The MOFs possessed an exceptionally high Eu adsorption capacity of 635 (91% removal), 642 (92% removal), and 628 mg g−1 (90% removal) for Cu-BTC, Ca-BTC, and Al-BTC, respectively, at pH 7 for an initial Eu concentration of 350 mg L−1. The MOFs were hydrolytically stable and possessed a high Eu adsorption capacity in a wide pH range of 4–8. While the pseudo-second-order model explained the adsorption kinetics, the adsorption process followed the Langmuir-Freundlich isotherms. The analysis confirmed that the Eu adsorption process was governed by chemical interactions between the carboxylic acid/carboxylate group and Eu(III) ions via complexation or ion exchange mechanism. A multi-metal adsorption study confirmed a preferential adsorption behaviour for trivalent lanthanides over divalent cations due to comparatively stronger interactions between Ln3+ ions and carboxylate groups. The XPS findings suggested Eu−OOC and Eu(OH)3 formed over the MOFs' surface after Eu adsorption. These MOFs were effectively regenerated for multiple cycles using 0.1 mol L−1 EDTA solution. Thus, the study demonstrated low-cost MOFs with superior regeneration capabilities for the capture of Eu(III) ions from waste solutions.

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing.

Fabrication of metal-organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus, far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal-organic frameworks (SURMOFs) has several requirements: mild conditions, low temperatures, day-long reaction times, and nonaggressive solvents. We herein present a fast method for the preparation of the MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50 and 2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. Scanning electron microscopy data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a poly(methyl methacrylate) layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as a Fabry-Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the ultraviolet-visible regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

Growth Control of Metal-Organic Framework Films on Marine Biological Carbon and Their Potential-Dependent Dopamine Sensing.

Ever-evolving advancements in films have fueled many of the developments in the field of electrochemical sensors. For biosensor application platforms, the fabrication of metal-organic framework (MOF) films on microscopically structured substrates is of tremendous importance. However, fabrication of MOF film-based electrodes always exhibits unsatisfactory performance, and the mechanisms of the fabrication and sensing application of the corresponding composites also need to be explored. Here, we report the fabrication of conformal MIL-53 (Fe) films on carbonized natural seaweed with the assistance of an oxide nanomembrane and a potential-dependent electrochemical dopamine (DA) sensor. The geometry and structure of the composite can be conveniently tuned by the experimental parameters, while the sensing performance is significantly influenced by the applied potential. The obtained sensor demonstrates ultrahigh sensitivity, a wide linear range, a low limit of detection, and a good distinction between DA and ascorbic acid at an optimized potential of 0.3 V. The underneath mechanism is investigated in detail with the help of theoretical calculations. This work bridges the natural material and MOF films and is promising for future biosensing applications.

Reactive Extrusion Printing for Simultaneous Crystallization-Deposition of Metal-Organic Framework Films.

Reactive extrusion printing (REP) is demonstrated as an approach to simultaneously crystallize and deposit films of the metal–organic framework (MOF) Cu3btc2 (btc=1,3,5‐benzenetricarboxylate), also known as HKUST‐1. The technique co‐delivers inks of the copper(II) acetate and H3btc starting materials directly on‐surface and on‐location for rapid nucleation into films at room temperature. The films were analyzed using PXRD, profilometry, SEM and thermal analysis techniques and confirmed high‐quality Cu3btc2 films are produced in low‐dispersity interconnected nanoparticulate form. The porosity was examined using gas adsorption which showed REP gives Cu3btc2 films with open interconnected pore structures, demonstrating the method bestows features that traditional synthesis does not. REP is a technique that opens the field to time‐efficient large‐scale fabrication of MOF interfaces and should find use in a wide variety of coating application settings.

Reactive Extrusion Printing for Simultaneous Crystallization‐Deposition of Metal–Organic Framework Films

Reactive extrusion printing (REP) is demonstrated as an approach to simultaneously crystallize and deposit films of the metal–organic framework (MOF) Cu3btc2 (btc=1,3,5-benzenetricarboxylate), also known as HKUST-1. The technique co-delivers inks of the copper(II) acetate and H3btc starting materials directly on-surface and on-location for rapid nucleation into films at room temperature. The films were analyzed using PXRD, profilometry, SEM and thermal analysis techniques and confirmed high-quality Cu3btc2 films are produced in low-dispersity interconnected nanoparticulate form. The porosity was examined using gas adsorption which showed REP gives Cu3btc2 films with open interconnected pore structures, demonstrating the method bestows features that traditional synthesis does not. REP is a technique that opens the field to time-efficient large-scale fabrication of MOF interfaces and should find use in a wide variety of coating application settings.

Proton conduction in two highly stable cadmium(II) metal-organic frameworks built by substituted imidazole dicarboxylates

Recently, the fabrication of metal-organic frameworks (MOFs) with high proton conductivity (σ) still attracts the attention of many researchers. Herein, a multifunctional organic ligand, 4-hydroxyphenyl-4,5-imidazole dicarboxylic acid (p-HOPhH3IDC) was adopted to solvothermally prepare two stable one-dimensional Cd(II) MOFs, {[Cd2(p-HOPhHIDC)2(phen)2]·H2O}n (1) (phen ​= ​1,10-phenanthroline), {[Cd2(p-HOPhHIDC)2(2,2′-bipy)2]·H2O}n (2) (2, 2′-bipy ​= ​2, 2′-bipyridine) in the presence of the N-containing ligands. Consequently, thermogravimetric analysis (TG), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM) determinations were employed to explore their structural stability. Importantly, their water-mediated proton conductivity demonstrated significant humidity- and temperature-dependence, increasing with the increase of both, and could attain the best value above 10−4 ​S ​cm−1 under 100 ​°C and 98% RH. The structural analyses along with the calculation of activation energy revealed that the rich H-bonded networks inside their frameworks are responsible for the higher proton conductivity. Finally, the proton-conducting mechanisms of the two MOFs were highlighted.

Remedy for Collapse of ZIF Derived Carbon: Micro-Pore Filled Synthesis to Improve ORR Catalytic Property

Zeolitic imidazolate framework (ZIF) derived carbons deliver outstanding performance as oxygen reduction reaction (ORR) catalysts. However, their electrocatalytic activities are limited due to unavoidable collapse of ZIFs upon pyrolysis, which results in degradation of porosity, sintering of metals and loss of active sites. In this work, a micro-pore filling strategy was employed to strength the architecture of ZIF by using size matched cyanamide molecules as fillers. The cyanamide with high nitrogen content shows a triple effect in stabilizing the carbonaceous skeleton, preserving of metal containing active sites and improving the conductivity of matrix. Therefore, the as-prepared Fe, Co co-doped ZIF derived carbon (FeCo@NC-N) delivers a significantly improved electrochemical activity for ORR than its unfilled counterpart, with half-wave potential upshifted by 30 mV (0.84 V vs RHE). Besides, a promoted power density of home-assembled zinc-air battery is obtained when FeCo@NC-N is applied as cathode catalyst. This work demonstrates a reliable approach to mitigate framework collapse of metal organic framework (MOF), thus may open a new way for fabrication of MOF based catalysts with increased loading of pores and active sites.

Synthesis, Characterization, and Application of Magnetized Lanthanum (III)-Based Metal-Organic Framework for the Organic Dye Removal from Water

A hybrid composite based on metal-organic framework (MOF) was chemically fabricated by embedding the magnetic Fe3O4 nanoparticles within amino-functionalized porous La-MOF (MOF/NH2) to produce a highly efficient and reusable composite of MOF/NH2/Fe3O4. Different proper techniques were used for the characterization of surface morphology and chemical arrangement of the prepared MOF/NH2/Fe3O4 composite. The characterization results using various techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer, Emmett, and Teller analysis (BET), and vibrating sample magnetometer (VSM) approved the successful fabrication of MOF with amino arms on its surface besides the well magnetization using magnetic nanoparticles. The MOF/NH2/Fe3O4 composite showed enhanced adsorption capacity (618 mg/g) toward methyl orange (MO) anionic dye which is higher than many commercial reported adsorbents due to the presence of many types of adsorption sites (NH2 groups and lanthanum sites), large surface area of MOF, and the synergetic effect of magnetic nanoparticles. Moreover, the MOF/NH2/Fe3O4 composite showed selective adsorption of MO dye from dye mixtures owing to the electrostatic attraction. Also, the MOF/NH2/Fe3O4 composite retained over 90% of its efficiency for the dye removal even after six successive cycles. So, the present study provided a practical strategy for the design of functional MOF hybrid composites. Furthermore, due to the adaptability of its architectural form, it is a potential adsorbent material for industrial wastewater treatment uses.

Meniscus Guided Coating and Evaporative Crystallization of UiO-66 Metal Organic Framework Thin Films

Thin-film fabrication of metal organic frameworks (MOFs) has been explored for a range of applications, including separations, catalysis, sensing, and charge transport. However, many fabrication te...

Decorating UiO-66-NH2 crystals on recyclable fiber bearing polyamine and amidoxime bifunctional groups via cross-linking method with good stability for highly efficient capture of U(VI) from aqueous solution

Although polyacrylonitrile fiber (PANF) and metal-organic frameworks (MOFs) have been extensively investigated to remove U(VI) from water, their practical applications are seriously hindered by the relatively low stability of PANF in acidic solution and great difficulty of separating MOFs nanoparticles from solution, beside that, little attention is paid to the fabrication of MOFs and PANF composite materials (MPCMs) with excellent adsorption capacity for U(VI). Herein, we report the synthesis of novel MPCMs by decorating different concentrations of UiO-66-NH2 crystals onto polyamine and amidoxime groups functionalized PANF (PA-AO-PANF) through cross-linking method for U(VI) extraction. The characterization results reveal that the combination of PA-AO-PANF and UiO-66-NH2 crystals endows MPCMs with excellent separation ability, large surface area, good stability and plentiful surface functional groups, which contributes to good selectivity and enhanced adsorption performance. Consequently, the obtained UN-PA-AO-PANF-2 shows the maximum uptake capacity of 441.8 mg/g and equilibrium uptake time of 30 min towards U(VI). Besides, the U(VI) uptake ability and structure of UN-PA-AO-PANF-2 are well preserved after ten adsorption-desorption cycles. With these outstanding properties, the adsorbent has great potential for the capture of U(VI) from aqueous solutions. Importantly, this work provides a cost-effective and efficient way to construct extremely stable MPCMs hybrid fibers.

All-in-one display device with multicolor states derived from NBU-3 MOF/monoalkylated viologen hybrid ionogel material

Recently, metal-organic frameworks (MOFs) have gained considerable attention for electrochromic (EC) applications owing to their improved electrochemical performance and superior processing ability. As a class of well-recognized organic EC materials, viologens are desirable and they are major active EC components for most of the marketed EC devices due to their structural versatility and property tunability. Over the past two decades, extensive efforts have been made to design and synthesize different types of viologen-based materials with enhanced EC properties. Herein, we report fabrication of MOFs and 1-hexyl-[4,4′-bipyridin]-1-ium bis (trifluoromethane sulfonyl) imide [MHV][TFSI] based all-in-one hybrid ionogel as an electrochromic device (ECD). The fabricated ECD showed reversible multicolor property with stability over 2000 cycles. Initially, the ECD showed light yellow color, and subsequently, it changed to light green, blue, and maroon color accordingly. The fabricated ECD displayed fast coloration time(tc), and bleaching times(tb) of 4.35 s and 7.72 s, respectively, along with a coloration efficiency of 99.14 cm2/C. The performance enhancement mechanisms are also concisely discussed in the present work. This work introduces the novel way to fabricate MOF based electrochromic ionogel (ECIG) ECDs and paves the way to the advancement of electrochromic ionogel-based display devices.

Porous Metal-Organic Framework Liquids for Enhanced CO2 Adsorption and Catalytic Conversion.

The unique applications of porous metal-organic framework (MOF) liquids with permanent porosity and fluidity have attracted significant attention. However, fabrication of porous MOF liquids remains challenging because of the easy intermolecular self-filling of the cavity or the rapid settlement of porous hosts in hindered solvents that cannot enter their pores. Herein, we report a facile strategy for the fabrication of a MOF liquid (Im-UiO-PL) by surface ionization of an imidazolium-functionalized framework with a sterically hindered poly(ethylene glycol) sulfonate (PEGS) canopy. The Im-UiO-PL obtained in this way has a CO2 adsorption approximately 14 times larger than that of pure PEGS. Distinct from a porous MOF solid counterpart, the stored CO2 in Im-UiO-PL can be slowly released and efficiently utilized to synthesize cyclic carbonates in the atmosphere. This is the first example of the use of a porous MOF liquid as a CO2 storage material for catalysis. It offers a new method for the fabrication of unique porous liquid MOFs with functional behaviors in various fields of gas adsorption and catalysis.

Porous Metal–Organic Framework Liquids for Enhanced CO2 Adsorption and Catalytic Conversion

AbstractThe unique applications of porous metal–organic framework (MOF) liquids with permanent porosity and fluidity have attracted significant attention. However, fabrication of porous MOF liquids remains challenging because of the easy intermolecular self‐filling of the cavity or the rapid settlement of porous hosts in hindered solvents that cannot enter their pores. Herein, we report a facile strategy for the fabrication of a MOF liquid (Im‐UiO‐PL) by surface ionization of an imidazolium‐functionalized framework with a sterically hindered poly(ethylene glycol) sulfonate (PEGS) canopy. The Im‐UiO‐PL obtained in this way has a CO2 adsorption approximately 14 times larger than that of pure PEGS. Distinct from a porous MOF solid counterpart, the stored CO2 in Im‐UiO‐PL can be slowly released and efficiently utilized to synthesize cyclic carbonates in the atmosphere. This is the first example of the use of a porous MOF liquid as a CO2 storage material for catalysis. It offers a new method for the fabrication of unique porous liquid MOFs with functional behaviors in various fields of gas adsorption and catalysis.

A Facile Method to Prepare Multifunctional Cotton Fabrics based on Zeolitic Imidazolate Framework

The fabrication of metal organic frameworks (MOFs) on the various supported substrates, especially lightweight and flexible substrates have been attempted for many years. In recent years, zeolitic imidazole frameworks (ZIF-8) and fabric composites have attracted researchers’ interest, but the combination of two-dimensional zeolitic imidazolate framework (ZIF-L) and fabric rarely involves. Aiming to this, a two-dimensional ZIF-L was successfully fixed on modified cotton fabrics by a facile in-situ growing method under the same experimental conditions as the synthesis of ZIF-8, and ZIF-L coated cotton fabric (CF-NH2@ZIF-L) has multiple properties like indoor formaldehyde purifying capability, excellent antibacterial properties and good UV protection. The cotton fabric was first modified with 3-aminopropyltrimethoxysilane (APTMS) and then the ZIF-L crystal films were in situ growth on the amine modified cotton fibers at room temperature in aqueous phase. The CF-NH2@ZIF-L fabric demonstrates excellent antibacterial properties and its antibacterial activity against Escherichia coli and Staphylococcus aureus is 99.52 % and 99.89 % respectively. In addition, it also has good UV protection and indoor formaldehyde purifying capability. The multifunctional cotton fabric prepared by this method can be viewed as a potential candidate used as decorative textile or air purification material.