Metal-organic Frameworks Surface Research Articles

Modulating the Conduction Band of MOFs by Introducing Tiny TiO2 Nanoparticles for Enhanced Photocatalytic Performance: Importance of the Loading Position.

The preparation of TiO2 and metal-organic framework (MOF) into composite photocatalysts has been proven to be a mature and effective strategy to achieve stronger catalytic activity. In this work, we focus on exploring the significant effects and mechanisms of the relative positions of decorated titanium oxide nanoparticles and MOFs on the final catalytic activity. We first used a simple in situ method to encapsulate tiny TiO2 nanoparticles into a Zr-MOF (PCN-222), where Zr-Ti bonds were created at the interface of the two components. Thanks to the strong interfacial interaction forces, band bending occurred in TiO2@PCN-222 and a more negative conduction band (Δ = 0.26 V) with better electron transport properties was obtained. The results of photocatalytic CO2 reduction experiments under visible light showed a 78% increase (142 μmol g-1 h-1) in the production rate of HCOO-. Surprisingly, the loading of TiO2 nanoparticles on the MOF surface (TiO2@PCN-222) resulted in a significant decrease of 56% in the catalyst yield activity due to poor adsorption and electron transfer properties. This work demonstrates the possibility of tuning the band structure and catalytic activity of MOFs with the help of changing the position of the dopant and shows the importance of the rational design of MOF-based composites.

Macrophage Cell Membrane Coating on Piperine-Loaded MIL-100(Fe) Nanoparticles for Breast Cancer Treatment

Piperine (PIP), a compound found in Piper longum, has shown promise as a potential chemotherapeutic agent for breast cancer. However, its inherent toxicity has limited its application. To overcome this challenge, researchers have developed PIP@MIL-100(Fe), an organic metal–organic framework (MOF) that encapsulates PIP for breast cancer treatment. Nanotechnology offers further treatment options, including the modification of nanostructures with macrophage membranes (MM) to enhance the evasion of the immune system. In this study, the researchers aimed to evaluate the potential of MM-coated MOFs encapsulated with PIP for breast cancer treatment. They successfully synthesized MM@PIP@MIL-100(Fe) through impregnation synthesis. The presence of MM coating on the MOF surface was confirmed through SDS-PAGE analysis, which revealed distinct protein bands. Transmission electron microscopy (TEM) images demonstrated the existence of a PIP@MIL-100(Fe) core with a diameter of around 50 nm, surrounded by an outer lipid bilayer layer measuring approximately 10 nm in thickness. Furthermore, the researchers evaluated the cytotoxicity indices of the nanoparticles against various breast cancer cell lines, including MCF-7, BT-549, SKBR-3, and MDA. The results demonstrated that the MOFs exhibited between 4 and 17 times higher cytotoxicity (IC50) in all four cell lines compared to free PIP (IC50 = 193.67 ± 0.30 µM). These findings suggest that MM@PIP@MIL-100(Fe) holds potential as an effective treatment for breast cancer. The study’s outcomes highlight the potential of utilizing MM-coated MOFs encapsulated with PIP as an innovative approach for breast cancer therapy, offering improved cytotoxicity compared to free PIP alone. Further research and development are warranted to explore the clinical translation and optimize the efficacy and safety of this treatment strategy.

Postsynthetische Photochemische Modifizierung und 2D Strukturierung von Zr‐MOF Dünnfilmen mit Benzophenon Linkermolekülen

AbstractFür die Herstellung von MOF‐basierten Bauteilen der nächsten Generation ist die Verfügbarkeit hochgradig anpassungsfähiger Materialien in geeigneten Formen entscheidend. In dieser Arbeit stellen wir Dünnfilme eines Metall‐organischen Gerüstes (MOF) mit photoreaktiven Benzophenon‐Brückenmolekülen vor. Kristalline, orientierte und poröse Filme des Zirkonium‐basierten bzpdc‐MOF (bzpdc=Benzophenon‐4‐4′‐dicarboxylat) können über direktes Wachstum auf Silizium‐ oder Glassubstraten hergestellt werden. Durch eine anschließende photochemische Modifizierung der Zr‐bzpdc‐MOF‐Filme lassen sich verschiedene Eigenschaften mittels kovalenter Anbindung von Modifizierungsreagenzien postsynthetisch einstellen. Neben der Modifizierung mit kleinen Molekülen sind auch grafting‐from Polymerisationsreaktionen möglich und in einer weiteren Ausbaustufe sogar die 2D‐Strukturierung und das Fotoschreiben definierter Strukturen; z.B. durch einen fotolithographischen Ansatz, der den Weg zu mikro‐strukturierten MOF‐Oberflächen ebnet.

Postsynthetic Photochemical Modification and 2D Structuring of Zr-MOF Thin Films Containing Benzophenone Linker Molecules.

For the fabrication of next-generation MOF-based devices the availability of highly adaptable materials in suitable shapes is crucial. Here, we present thin films of a metal-organic framework (MOF) containing photoreactive benzophenone units. Crystalline, oriented and porous films of the zirconium-based bzpdc-MOF (bzpdc=benzophenone-4-4'-dicarboxylate) are prepared by direct growth on silicon or glass substrates. Via a subsequent photochemical modification of the Zr-bzpdc-MOF films, various properties can be tuned postsynthetically by covalent attachment of modifying agents. Apart from the modification with small molecules, also grafting-from polymerization reactions are possible. In a further extension, 2D structuring and photo-writing of defined structures is also possible, for example by using a photolithographic approach, paving the way towards micro-patterned MOF surfaces.

Silane-Functionalized Metal-Organic Frameworks for Stimuli-Responsive Drug Delivery Systems: A New Universal Strategy.

A new universal strategy for silane functionalization of metal-organic frameworks (MOFs) was developed. It was demonstrated that silanes were coupled both with terminal hydroxyl (OH) groups and with bridging OH groups of metal-oxo clusters of MOFs through condensation reactions between the silanols of hydrolyzed silanes and the terminal/bridging OH groups to form metal-O-Si bonds. A wide variety of functionalization of MOFs with conventional silanes can be realized by combining synthesis reactions in the solution phase and chemical modifications on the surface. Multivalent supramolecular nanovalves based on the host-guest chemistry of cyclodextrin polymer (CDP) and benzimidazole stalks silanized on the nanoscale MOF (NMOF) surface were successfully constructed. The CDP-valved NMOFs showed the excellent performance of low pH- and α-amylase-responsive controlled drug release. In vitro and in vivo results demonstrated that the CDP-valved NMOFs had a significant inhibitory effect on tumor growth and almost no damage/toxicity to normal tissues. The silanization strategy is universal and opens up a new way for the functionalization of MOFs, which are endowed with a wide variety of applications spanning gas storage, chemical sensing, adsorption and separation, heterogeneous catalysis, and drug delivery.

Constructing cactus-like mixed dimensional MOF@MOF as sorbent for extraction of bisphenols from environmental water

Metal-organic frameworks (MOFs) received considerable attention to adsorption and removal of various environmental pollutants because of some inherent advantages. However, it is challenging but meaningful to design and fabricate hierarchical mixed-dimensional MOFs with synergistic effects to enhance the performance for removal and preconcentration of environmental pollutants. Herein, a new hierarchical two-dimensional (2D)-three-dimensional (3D) mixed-dimensional cactus‐like MOF@MOF hybrid material (PCN-134@Zr-BTB) was prepared by in-situ growth of 2D MOF nanosheets (Zr-BTB) on the surface of 3D MOF (PCN-134). The PCN-134@Zr-BTB composites combine the advantages of 2D and 3D MOFs with extensive mesoporous structures and large surface area for effective removal and enrichment of bisphenols (BPs). In comparison with pristine PCN-134 and Zr-BTB materials, the PCN-134@Zr-BTB hybrid material presented excellent adsorption performance for BPs. The adsorption isotherms are consistent with the Langmuir model, and the maximum adsorption capacity of four bisphenols (BPs) ranged from 135.1 mg/g to 628.9 mg/g. The adsorption kinetics are in accordance with the pseudo-second-order model. The recoveries ranged from 72.8% to 108%. The limits of detection were calculated at 0.02–0.03 ng/mL. The enrichment factors were calculated in the range of 310–374. According to FT-IR and XPS analysis, the main adsorption mechanisms are hydrogen bonding and π-π stacking. Nevertheless, this work provides a new and convenient strategy for the preparation of new hierarchical mixed-dimensional MOF@MOF (PCN-134@Zr-BTB) hybrid material for extraction and enrichment of BPs from aqueous matrix.

Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions.

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported copper(I) photocatalyst for multiple iminyl radical-mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post-synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF-based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.

Metal‐Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical‐Mediated Reactions

AbstractVisible‐light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine‐ligated copper(I) complexes, we describe herein an effective metal‐organic framework (MOF)‐supported copper(I) photocatalyst for multiple iminyl radical‐mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post‐synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF‐based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition‐metal photoredox catalysis.

Visible-light-harvesting basolite-A520 metal organic framework for photocatalytic hydrogen evolution

A heterogeneous photosensitizer Ru@dpdhpzBASF-A520 has been successfully synthesized following an unprecedented strategy based on the incorporation of surface dipyridyl-dihydropyridazine adducts by Diels–Alder reaction on the aluminum fumarate units of the highly porous metal-organic framework (MOF) BASF-A520 and their further coordination to ruthenium metal centers. The characterization of the resulting metal-organic framework, including the ruthenium bipyridine-like photosensitizer moieties attached to its linkers, has been carried out by a wide variety of techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance (13C CP/MAS NMR), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible (UV–vis) spectroscopy. The light absorption in the visible region shown by the resulting material, Ru@dpdhpzBASF-A520, has allowed its application as a single-site solid photosensitizer for photochemical reactions of hydrogen evolution in conjunction with Pt nanoparticles as catalyst, EDTA as sacrificial electron donor and MV as electron carrier. A remarkable photocatalytic activity after 72 h was achieved, with a TON of 1157 based on the heterogeneous ruthenium photosensitizer, in aqueous solution at pH 5.0, which confirmed the effective stabilization of the ruthenium dipyridyl-dihydropyridazine adducts on the MOF surface and the efficient electron injection from the photoexcited Ru@dpdhpzBASF-A520 to Pt nanoparticles mediated by MV electron carrier for hydrogen generation from water.

Conformational changes and location of BSA upon immobilization on zeolitic imidazolate frameworks

The location and the conformational changes of proteins/enzymes immobilized within Metal Organic Frameworks (MOFs) are still poorly investigated and understood. Bovine serum albumin (BSA), used as a model protein, was immobilized within two different zeolitic imidazolate frameworks (ZIF-zni and ZIF-8). Pristine ZIFs and BSA@ZIFs were characterized by X-ray diffraction, small-angle X-ray scattering, scanning electron microscopy, confocal laser scanning microscopy, thermogravimetric analysis, micro-FTIR and confocal Raman spectroscopy to characterize MOFs structure and the protein location in the materials. Moreover, the secondary structure and conformation changes of BSA after immobilization on both ZIFs were studied with FTIR. BSA is located both in the inner and on the outer surface of MOFs, forming domains that span from the micro- to the nanoscale. BSA crystallinity (β-sheets + α-helices) increases up to 25 % and 40 % due to immobilization within ZIF-zni and ZIF-8, respectively, with a consequent reduction of β-turns.

MOF as nanoscale drug delivery devices: Synthesis and recent progress in biomedical applications

Metal-organic frameworks (MOFs) have received a lot of attention for application as nanoscale drug delivery devices due to their unique properties in high storage capacities, multiple functionalities, and excellent biocompatibilities. and abundant functionalities. Several strategies can be used to synthesise including traditional reactions (solvothermal or non-solvothermal methods), microwaves, electrochemistry, sonochemistry, mechanochemistry. MOFs are composed of metal ions/metal clusters linked by multitopic organic ligands containing sulfonate, carboxylate, and phosphonate groups. The various methods for modifying the surfaces of MOFs are described with covalent bonds and covalent bonds. The application of functional groups, MOFs are developed to produce high porous materials through covalent and non-covalent bonds. MOFs are used to encapsulate various drugs and other macromolecules including nucleic acids, DNA, siRNA and properties.

Challenges in Developing MOF-Based Membranes for Gas Separation.

Metal-organic frameworks (MOFs) are promising candidates for membrane gas separation. MOF-based membranes include pure MOF membranes and MOF-based mixed matrix membranes (MMMs). This Perspective discusses the challenges for the next stage of the development of MOF-based membranes based on research conducted in the past decade. We focused on three major issues associated with pure MOF membranes. First, some MOF compounds have been overstudied, despite the availability of numerous MOFs. Second, gas adsorption and diffusion in MOFs are often independently investigated. The correlation between adsorption and diffusion has seldom been discussed. Third, we identify the importance of characterizing the gas distribution in MOFs to understand the structure-property relationships for gas adsorption and diffusion in MOF membranes. For MOF-based MMMs, engineering the MOF-polymer interface is essential for achieving the desired separation performance. Various approaches to modify the MOF surface or polymer molecular structure have been proposed to improve the MOF-polymer interface. Herein, we present defect engineering as a facile and efficient approach for engineering the MOF-polymer interfacial morphology and its extended application for various gas separations.

MOFs-Modified Electrochemical Sensors and the Application in the Detection of Opioids.

Opioids are widely used in clinical practice, but drug overdoses can lead to many adverse reactions, and even endanger life. Therefore, it is essential to implement real-time measurement of drug concentrations to adjust the dosage given during treatment, keeping drug levels within therapeutic levels. Metal-Organic frameworks (MOFs) and their composite materials modified bare electrode electrochemical sensors have the advantages of fast production, low cost, high sensitivity, and low detection limit in the detection of opioids. In this review, MOFs and MOFs composites, electrochemical sensors modified with MOFs for the detection of opioids, as well as the application of microfluidic chips in combination with electrochemical methods are all reviewed, and the potential for the development of microfluidic chips electrochemical methods with MOFs surface modifications for the detection of opioids is also prospected. We hope that this review will provide contributions to the study of electrochemical sensors modified with MOFs for the detection of opioids.

Post-Synthetic Surface Modification of Metal-Organic Frameworks and Their Potential Applications.

Metal-organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance. This article summarizes different types of post-synthetic modifications and possible applications of modified materials such as: catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids.

Based on coordination modulation to improve the colloidal stability of two-dimensional metal–organic framework

Two-dimensional metal–organic frameworks (MOFs) have emerged as an attractive type of 2D materials, especially in surface-dependent reactions. And the colloidal stability of 2D MOF is crucial to its performance in surface-dependent application. This work provides a facile approach for directly fabricating 2D MOF with good colloidal stability by introducing monotopic ligand as modulator through coordination modulation. Modulator with methoxy group can effectively decrease the size of 2D MOF nanosheet and selectively modify MOF surface to improve its colloidal stability without changing its nanosheet morphology and porous crystal structure. The well-dispersed 2D MOFs provide more active specific surface area, which shows excellent catalytic performance in the synthesis of Schiff base. This method paves a new way to fabricate MOF-based materials with remarkable performances for surface-dependent application.

Ab Initio Study of Adsorption of Polymers on Metal–Organic Framework Surfaces

We present a computational study of metal–organic framework (MOF)/polymer interfaces in order to better understand the phenomena relevant to optimizing the design of MOF/polymer mixed-matrix membrane (MMM) materials. In this pursuit, we study adsorption of models of polymers Kapton and 6FDA-Durene to models of MOF surfaces both with and without coordinatively unsaturated metal sites existing on the surface (ZIF-8 and Co-BDC, respectively) at the density functional theory (DFT) level. To do this, we develop and tune models of polymers that are DFT-accessible, establishing a method for creating models of polymers that is transferable beyond these systems for use in studying MMMs, identifying some limits to this method. Through this work, we find that while polymer interactions with MOF surfaces may be expected to be dispersion-dominated, in the presence of coordinatively unsaturated metals on the surface, electronic and electrostatic effects may play a significant role, consistent with the previous literature in this area. We additionally find that while polymer model terminations often do not strongly affect the qualitative behavior at the MOF/polymer interface, an accurate electronic representation of the polymers may be critical for the development of force field-based tools to model MMMs and for a detailed understanding of the interactions in some cases.

Polydopamine-guarded metal-organic frameworks as co-delivery systems for starvation-assisted chemo-photothermal therapy

Cutting off glucose provision by glucose oxidase (GOx) to famish tumors can be an assistance with chemotherapy to eliminate cancer cells. Co-encapsulation of GOx and chemotherapeutics (doxorubicin) within pH-sensitive metal-organic frameworks (MOFs) could disorder metabolic pathways of cancer cells and generate excessive intracellular reactive oxygen species (ROS), together. To prevent premature leach of GOx from the porous channels of MOFs, polydopamine (PDA) was deposited on the surface of MOFs, which endowed the delivery system with photothermal conversion ability. Our nanoscaled co-delivery system (denoted as DGZPNs) remains stable with low amount of drug leakage under simulated physiological conditions in vitro and internal environment, while they are triggered to release doxorubicin (DOX) and GOx in acid tumor microenvironment and at high temperature for reinforced chemotherapy. NIR laser irradiation also activates superior photothermal conversion efficiency of PDA (36.9 %) to initiate hyperthermia to ablate tumor tissue. After being phagocytized by 4 T1 cells (breast cancer cells), the DGZPNs delivery system showed a superior therapeutic efficacy with a tumor growth inhibition of 88.9 ± 6.6 % under NIR irradiation, which indicated that the starvation-assisted chemo-photothermal therapy prompts the significant advance of synergistic therapy in a parallelly controlled mode.

Facet-Dependent Photocatalytic Behavior of Fe-soc-MOF for Carbon Dioxide Reduction.

Exposing different facets on metal-organic frameworks (MOFs) is an efficient approach to regulate their photocatalytic performance for CO2 reduction. Herein, Fe-soc-MOFs exposed with different facets were successfully synthesized, and the morphologies of Fe-soc-MOF exposed with eight {111} facets (Fe-soc-O) and that exposed with eight {111} and six {100} crystal facets (Fe-soc-M) are first reported. Fe-soc-MOFs have facet-dependent active sites on their surface and correspondingly different catalytic performance for photocatalytic CO2 reduction. Fe-soc-O has the highest CO production of 1804 μmol g-1 h-1, while the Fe-soc-MOF exposed with six {100} facets (Fe-soc-C) has the best CO selectivity of 94.7%. Density functional theory (DFT) calculations demonstrate that the (111) facet has more favorable thermodynamic potential for CO2 reduction and H2 evolution compared with the (100) one, deriving from its facet-dependent active sites. This work shows that utilizing the facet-engineering strategy to regulate the active sites exposed on the surface of MOFs is feasible. The results display the relation between the facet of MOFs and the photocatalytic behavior for CO2 reduction.

Metal organic framework/covalent organic framework composite for solid-phase microextraction of polycyclic aromatic hydrocarbons in milk samples

Based on the excellent physicochemical properties of metal organic framework (MOF) and covalent organic framework (COF), a novel MOF/COF composite was designed and prepared as coating fiber for headspace solid-phase microextraction (HS-SPME). Based on the amino group on the surface of as-synthesized UiO-66-NH2, porphyrin-based COF was covalently grown on the MOF surface by using tetra(4-aminophenyl)porphyrin and 4,4′-biphenyldicarboxaldehyde as building blocks to fabricate a novel MOF/COF composite. Subsequently, the composite was physically coated on the surface of polished stainless-steel wire for HS-SPME of polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-flame ionization detection (GC-FID) determination. The morphology and structure of the MOF/COF composite was characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and N2 adsorption–desorption. Influential adsorption and desorption parameters were optimized and the extraction mechanism was also discussed. Under optimal conditions, an HS-SPME/GC-FID method based on MOF/COF composite coated fiber was established for the analysis of PAHs in milk samples. The linear ranges of this method were 0.2–50.0 ng mL−1 (R2 > 0.9908), and the limits of detection and quantitation were in the range of 0.02–0.07 ng mL−1 and 0.07–0.24 ng mL−1, respectively. The relative standard deviations (RSDs) for PAHs were all less than 7.05 %, which indicated eminent repeatability and reproducibility of the established method. Besides, the enrichment factors for PAHs were relatively high in the range of 2003 to 7763, and the recoveries for milk samples were ranged from 85.43 % to 115.8 % with satisfactory RSDs of 0.92–9.00 %.

Design of enzyme@metal organic framework composites with thermo-responsivity for colourimetric detection of glucose.

Enzyme immobilization on metal-organic frameworks (MOFs) has interested researchers in recent decades due to the outstanding characteristics of MOFs. However, despite some enzyme@MOF composites exhibiting better tolerance, stability and catalysis than free enzymes, boosting the catalytic performance of stimuli-responsive polymer-grafted MOFs composites remains a challenging task. Herein, a glucose oxidase (GOx)-horseradish peroxidase (HRP)@MOF (UiO-66-NH2, U)@polymer composite with tunable catalytic ability was constructed by modification with thermo-responsive poly(N-isopropylacrylamide) (PN) via a surface-selective post-synthetic protocol. Temperature increases changed the PN-based soft armour from a "stretch" to a "coil" conformation on the MOF surface, resulting in the confinement effect and boosting the catalytic performance of the GOx-HRP@U@PN composites. Compared with its maximum catalytic reaction rate at 25 °C, the proposed composites showed 18-fold improvement in catalytic performance at 37 °C. Additionally, a colourimetric method for serum glucose analysis was developed using a GOx-HRP-based catalytic cascade reaction with a linear range from 0.1 to 2.0 mM and a low detection limit of 0.03 mM. Remarkably, the surface PN-shell-based soft armour proved to be the key factor for enhancing the catalytic performance of the as-designed composites. The co-immobilization of GOx-HRP onto the thermo-responsive U@PN surface provides a new approach for the development of highly sensitive colourimetric glucose sensing protocols.