Porous Metal-organic Frameworks Research Articles

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.

Degradation and Erosion of Metal-Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System.

To make a drug work better, the active substance can be incorporated into a vehicle for optimal protection and control of the drug delivery time and space. For making the drug carrier, the porous metal-organic framework (MOF) can offer high drug-loading capacity and various designs for effective drug delivery performance, biocompatibility, and biodegradability. Nevertheless, its degradation process is complex and not easily predictable, and the toxicity concern related to the MOF degradation products remains a challenge for their clinical translation. Here, we describe an in-depth molecular and nanoscale degradation mechanism of aluminum- and iron-based nanoMIL-100 materials exposed to phosphate-buffered saline. Using a combination of analytical tools, including X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, small-angle X-ray scattering, and electron microscopy, we demonstrate qualitatively and quantitatively the formation of a new coordination bond between metal(III) and phosphate, trimesate release, and correlation between these two processes. Moreover, the extent of material erosion, i.e., bulk or surface erosion, was examined from the transformation of nanoparticles' surface, morphology, and interaction with water. Similar analyses show the impact of drug loading and surface coating on nanoMIL-100 degradation and drug release as a function of the metal-ligand binding strength. Our results indicate how the chemistry of nanoMIL-100(Al) and nanoMIL-100(Fe) drug carriers affects their degradation behaviors in a simulated physiological medium. This difference in behavior between the two nanoMIL-100s enables us to better correlate the nanoscale and atomic-scale mechanisms of the observed phenomena, thus validating the presented multiscale approach.

Metal–organic framework-catalyzed selective oxidation of alcohols and oxidative cross-coupling for C–C and C–N bond-forming reactions

A novel porous metal–organic framework Co(btc)(bpy) (Co-MOF-3a) was synthesized by employing a bipyridyl ligand, benzene tricarboxylic acid, and Co(NO3)2·6H2O and was completely characterized.

Fluoro-bridged rare-earth metal-organic frameworks.

Rare-earth (RE) metal-organic frameworks (MOFs) offer unique optical, electronic, and magnetic properties. RE metals tend to make binuclear metal nodes resulting in dense nonporous coordination networks. Three dimensional porous RE-MOFs have been reported by preparing bigger metal nodes based on metal clusters often found as hexaclusters or nonaclusters. The formation of metal clusters (>2 metal ions) generally requires the use of fluorinated organic molecules reported as modulators. However, it was recently discovered that these molecules are not modulators, rather they act as reactants and leave fluorine in the metal clusters. The formation and types of fluorinated RE metal clusters have been discussed. These fluorinated clusters offer higher connectivity which results in porous MOFs. The presence of fluorine in these metal clusters offers unique properties, such as higher thermal stability and improved fluorescence. This frontier summarizes recent progress and gives future perspective on the fluorinated metal clusters in the RE-MOFs.

Endogenous metal-ion dynamic nuclear polarization for NMR signal enhancement in metal organic frameworks.

Rational design of metal-organic framework (MOF)-based materials for catalysis, gas capture and storage, requires deep understanding of the host-guest interactions between the MOF and the adsorbed molecules. Solid-State NMR spectroscopy is an established tool for obtaining such structural information, however its low sensitivity limits its application. This limitation can be overcome with dynamic nuclear polarization (DNP) which is based on polarization transfer from unpaired electrons to the nuclei of interest and, as a result, enhancement of the NMR signal. Typically, DNP is achieved by impregnating or wetting the MOF material with a solution of nitroxide biradicals, which prevents or interferes with the study of host-guest interactions. Here we demonstrate how Gd(iii) ions doped into the MOF structure, LaBTB (BTB = 4,4',4''-benzene-1,3,5-triyl-trisbenzoate), can be employed as an efficient polarization agent, yielding up to 30-fold 13C signal enhancement for the MOF linkers, while leaving the pores empty for potential guests. Furthermore, we demonstrate that ethylene glycol, loaded into the MOF as a guest, can also be polarized using our approach. We identify specific challenges in DNP studies of MOFs, associated with residual oxygen trapped within the MOF pores and the dynamics of the framework and its guests, even at cryogenic temperatures. To address these, we describe optimal conditions for carrying out and maximizing the enhancement achieved in DNP-NMR experiments. The approach presented here can be expanded to other porous materials which are currently the state-of-the-art in energy and sustainability research.

Polarity profiling of porous architectures: solvatochromic dye encapsulation in metal-organic frameworks.

Metal-organic frameworks (MOFs) have gathered significant interest due to their tunable porosity leading to diverse potential applications. In this study, we investigate the incorporation of the fluorosolvatochromic dye 2-butyl-5,6-dimethoxyisoindoline-1,3-dione ([double bond, length as m-dash]Phth) into various MOF structures as a means to assess the polarity of these porous materials. As a purely inorganic compound, zeolite Y was tested for comparison. The fluorosolvatochromic behavior of Phth, which manifests as changes in its emission spectra in response to solvent polarity, provides a sensitive probe for characterizing the local environment within the MOF pores. Through systematic variation of the MOF frameworks, we demonstrate the feasibility of using (fluoro-)solvatochromic dyes as probes for assessing the polarity gradients within MOF structures. Additionally, the fluorosolvatochromic response was studied as a function of loading amount. Our findings not only offer insights into the interplay between MOF architecture and guest molecule interactions but also present a promising approach for the rational design and classification of porous materials based on their polarity properties.

Close-packing effect of water clusters within metal-organic framework pores on proton conductivity: a dielectric relaxation phenomenon in loose space and colossal dielectric permittivity.

Proton-conducting metal-organic frameworks (MOFs) have attracted tremendous attention for their promising application in proton-exchange membrane fuel cells. Water clusters play an extremely important role in the proton-conduction process and affect the proton conductivity of host materials. To date, the close-packing effect of water clusters within pores on proton conductivity due to the amorphous structure of commercial proton-exchange membranes is unclear. Herein, we prepared two crystalline MOFs containing different water clusters, namely, [Sm2(fum)3(H2O)4]·3H2O (Sm-fum-7H2O) and [Er2(fum)3(H2O)4]·8H2O (Er-fum-12H2O) (H2fum = fumaric acid), and regulated their proton conductivities by changing the water clusters. As expected, Sm-fum-7H2O showed a high proton conductivity of 6.89 × 10-4 S cm-1 at 333 K and ∼97% RH because of the close packing of the water clusters within the pores triggered by a lanthanide contraction effect, outperforming that of Er-fum-12H2O and some previously reported MOFs. Additionally, Sm-fum-7H2O and Er-fum-12H2O demonstrated high dielectric functions, reaching 2.22 × 103 and 1.42 × 105 at 102.5 Hz, respectively, making Er-fum-12H2O a highly dielectric material. More importantly, broadband dielectric spectroscopy measurements indicated that there was a dielectric relaxation process in Er-fum-12H2O with an activation energy of 0.59 eV. The present findings provide a better understanding of the crucial role of confined water clusters in proton conductivity and the novel phenomenon of the coexistence of proton conduction and dielectric relaxation in crystalline MOF materials.

One-pot in situ synthesis of an NS-ligand co-doped metal-organic framework for the enhanced adsorption-assisted photocatalytic decontamination of metronidazole.

Doping active agents into metal-organic frameworks (MOFs) is widely sought after owing to its potential to enhance adsorption and photocatalytic efficiency, surpassing the potential of bare frameworks. This study incorporated a catalytically active NS-ligand (1,2-benzisothiazolin-3-one) into a very stable and porous PCN-600 MOF via an in situ synthesis approach. The NS-ligand, which matched with the host ligands of PCN-600, enabled the highly efficient synthesis of NS-co-doped MOFs. The pristine PCN-600 framework and morphology were retained in the MOF altered with the NS-ligand, as demonstrated by XRD, FTIR, and SEM characterizations. A high electron density was generated due to the synergistic effect between the defects in the NS-co-doped photocatalyst and engineered active sites. This facilitated the adsorption-assisted photocatalytic decontamination of metronidazole with an 87% removal by PCN-600-NS-10 compared to 43% by pristine PCN-600 within a total time of 150 min. The MOF doped with the NS-ligand exhibited a reduced band gap and enhanced adsorption and photocatalytic capabilities compared to pristine PCN-600. The impact of operational parameters, such as catalyst dosage, initial solution pH, and MNZ concentration, was also explored. Pseudo-second and pseudo-first order models were found to describe the adsorption and degradation kinetics of metronidazole and the Dubinin-Radushkevich model was found to fit the equilibrium adsorption results. The thermodynamic characteristics of adsorption processes (ΔGads, ΔHads, and ΔSads) demonstrated that adsorption was physical, spontaneous, and exothermic and resulted in increased entropy.

Computer analysis of the nitrogen adsorption process on MIL-53(Al) metal–organic frameworks

This paper evaluates the effect of different synthesis conditions on the structural properties of the porous metal–organic frameworks MIL-53(Al) produced by the microwave method at different reaction temperatures and times.

Stepwise construction of coordinative linkages and dynamic covalent linkages for a porous metal-organic framework.

A cyclic trinuclear complex is synthesized from AgI and 1H-pyrazole-4-carbaldehyde. Reticulation of the complex with 1,3,5-tris(4-aminophenyl)benzene through Schiff-base reaction affords a porous FDM-72 framework. Amine choice is systematically investigated as it may initiate metal reduction. This study proposes a new route and its amine selection criterion to synthesize Ag-based frameworks.

A magnesium phosphonate metal-organic framework showing excellent performance for lead(II) sensing and removal from aqueous solutions.

A hydrogen-bonded three-dimensional porous metal-organic framework [Mg(H2PCD)2(H2O)2]·2H2O (denoted as Mg-MOF·2H2O; H3PCD = 9-(2-(ethoxy(hydroxy)phosphonyl)ethyl)-9H-carbazole-3,6-dicarboxylic acid) was synthesized by the reactions of H3PCD and Mg(II) under solvothermal conditions. The free carboxylate group was maintained in the pore surface by adjusting the acidic reaction conditions. The highly stable Mg-MOF exhibits excellent performance for lead(II) sensing and removal from aqueous solutions.

A linker selective retention strategy to construct hierarchical porous metal-organic frameworks with high catalytic activity for oxidative desulfurization.

In order to improve the oxidative desulfurization (ODS) performance of MOF materials, an effective way is to convert a microporous MOF into a hierarchical porous MOF (HP-MOF) by utilizing the linker selective retention strategy. Herein, UiO-66 with the introduction of an unstable linker ligand (dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate, dhtz) can selectively remove dhtz ligands to form HP-MOF (HP-UiO-66-dhtz) through heat treatment at high temperature. While maintaining the original structure of UiO-66, HP-UiO-66-dhtz features mesopores and abundant Lewis acid sites, showing excellent ODS performance for diphenylthiophene (DBT).

Fenton reaction-driven pro-oxidant synergy of ascorbic acid and iron oxide nanoparticles in MIL-88B(Fe)

Firstly Fe3O4-MIL-88B(Fe) was studied, and the pro-oxidant role of ascorbic acid in enhancing its catalytic properties is investigated.

Tunable ratiometric temperature sensors based on a Zn-MOF material incorporating luminescent polyoxometalates and carbon dots

Incorporation of Eu polyoxometalates and carbon dots into a Zn-MOF matrix represents an efficient strategy to build luminescent ratiometric thermometers.

Electron Spin Resonance Spin Probe Technique for Investigating Non‐TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex

An ESR spin probe technique with non‐TEMPO radicals, such as nitronyl nitroxide (NN), benzonitronyl nitroxide (BzNN), and iminonitroxide (IN) radicals, was used for a porous metal‐organic framework (MOF), [(ZnI2)3(TPT)2] (ZnTPT; TPT = tris(4‐pyridyl)‐1,3,5‐triazine), at room temperature. The principal values of g and hyperfine coupling (A) tensors estimated from spectral reproduction were different from those for organic matrices for some of these radicals. These results indicate that host‐guest interactions occur between the ZnTPT matrix and guest radicals. Thus, when using NN, BzNN, and IN radicals as spin probes for a porous MOF, the interaction between the metal atoms or organic ligands in host materials and guest radicals should be considered. The experimental ESR spectra for the derivatives of NN or BzNN radicals were reproduced only by the rigid‐limit component in the ESR time scale. However, those for the derivatives of IN radicals were approximately reproduced only by rotational diffusion around the z‐axis perpendicular to the plane in the IN group. Interestingly, this reproduction was not around the y‐axis of the principal axes of the g tensors, parallel to the molecular long axis, as previously observed in a few organic matrices. The IN radicals dispersed in the ZnTPT matrix are expected to be accommodated in cylindrical or pseudocylindrical nanospaces sandwiched by the pyridyl or triazine rings of TPT in ZnTPT. These findings show that the ESR spin probe technique using non‐TEMPO radicals can be used to investigate the chemical and biological structures of nanosized materials.

Surface engineered metal-organic framework-based electrochemical biosensors for enzyme-mimic ultrasensitive detection of glucose: recent advancements and future perspectives.

Metal-Organic Frameworks (MOFs) have garnered significant attention in the development of electrochemical glucose sensors due to their unique and advantageous properties. The highly tunable pore channels of MOFs facilitate optimal diffusion of glucose molecules, while their large specific surface area provides abundant active sites for electrochemical reactions. Furthermore, the well-dispersed metallic active sites within MOFs enhance electrocatalytic activity, thereby improving the sensitivity and selectivity of glucose detection. These features make MOF-based nanoarchitectures promising candidates for the development of efficient and sensitive glucose sensors, which are crucial for diabetes management and monitoring. The integration of enzymatic biosensors with nanotechnology continues to drive advancements in glucose monitoring, offering the potential for more accurate, convenient, and user-friendly tools for diabetes management. Current research explores non-invasive glucose monitoring methods, such as using sweat, saliva, or interstitial fluid instead of blood, aiming to reduce the discomfort and inconvenience associated with frequent blood sampling. A review of the advancements and applications of MOF-based enzyme-mimic electrochemical sensors for glucose monitoring can provide valuable insights for young researchers, inspiring future research in biomedical device fabrication. Such reviews not only offer a comprehensive understanding of the current state of the art but also highlight existing challenges and future opportunities in the field of enzyme-less glucose sensing, particularly in the surface modification techniques of highly porous MOFs. This fosters innovation and new research directions. By understanding the advantages, challenges, and opportunities, researchers can contribute to the development of more effective and innovative enzyme-mimic glucose sensing transducers, which are essential for advancing biomedical devices.

Modulating confinement space in metal-organic frameworks enables highly selective indole C3-formylation.

Here, Selective C3-formylation of indole was achieved under mild conditions using a metal-organic framework (MOF) catalyst. The confined reaction space within the MOF pores effectively suppressed undesired side reactions and promoted the formation of the targeted product by controlling the reaction pathway. Density functional theory (DFT) calculations corroborated the experimental observations.

In situ growth of Zr-based metal-organic frameworks on cellulose sponges for Hg2+ and methylene blue removal

Metal-organic frameworks (MOFs) are characterised by high porosity levels and controllable structures, making them ideal adsorbents for wastewater. However, obtaining substrate materials with mechanical stability, excellent pore accessibility, and good processability for compositing MOF crystal powders to adsorb multiple pollutants in complex aqueous environments is challenging. In this study, porous MOFs@ modified cellulose sponge (MCS) composites were fabricated using MCS as a scaffold to provide anchoring sites for the coordination of Zr4+ ions and further in situ synthesis of MOFs, namely UiO-66@MCS and UiO-66-NH2@MCS, which effectively removed heavy metal ions and organic dyes. MOFs@MCS composites exhibit excellent water and dimensional stability, maintaining the pore structure by ambient drying during reuse. Compared with UiO-66@MCS composite, UiO-66-NH2@MCS composite exhibited a higher adsorption capacity of 224.5 mg·g−1 for Hg2+ and 400.9 mg·g−1 for methylene blue (MB). The adsorption of Hg2+ onto the MOFs@MCS composites followed the Langmuir and pseudo-second-order models, whereas the Freundlich and pseudo-second-order models were more suitable for MB adsorption. Moreover, the MOFs@MCS composites exhibited excellent reusability and were selective for the removal of Hg2+. Overall, this approach effectively combines Zr-based MOFs with mechanically and dimensionally stable porous cellulose sponges, rendering the approach suitable for purifying complex wastewater.

Design Principles Guiding Solvent Size Selection in ZIF-Based Type 3 Porous Liquids for Permanent Porosity.

Porous liquids (PLs), which are solvent-based systems that contain permanent porosity due to the incorporation of a solid porous host, are of significant interest for the capture of greenhouse gases, including CO2. Type 3 PLs formed by using metal-organic frameworks (MOFs) as the nanoporous host provide a high degree of chemical turnability for gas capture. However, pore aperture fluctuation, such as gate-opening in zeolitic imidazole framework (ZIF) MOFs, complicates the ability to keep the MOF pores available for gas adsorption. Therefore, an understanding of the solvent molecular size required to ensure exclusion from MOFs in ZIF-based Type 3 PLs is needed. Through a combined computational and experimental approach, the solvent-pore accessibility of exemplar MOF ZIF-8 was examined. Density functional theory (DFT) calculations identified that the lowest-energy solvent-ZIF interaction occurred at the pore aperture. Experimental density measurements of ZIF-8 dispersed in various-sized solvents showed that ZIF-8 adsorbed solvent molecules up to 2 Å larger than the crystallographic pore aperture. Density analysis of ZIF dispersions was further applied to a series of possible ZIF-based PLs, including ZIF-67, -69, -71(RHO), and -71(SOD), to examine the structure-property relationships governing solvent exclusion, which identified eight new ZIF-based Type 3 PL compositions. Solvent exclusion was driven by pore aperture expansion across all ZIFs, and the degree of expansion, as well as water exclusion, was influenced by ligand functionalization. Using these results, a design principle was formulated to guide the formation of future ZIF-based Type 3 PLs that ensures solvent-free pores and availability for gas adsorption.

Enhancing CO2 Hydrogenation Using a Heterogeneous Bimetal NiAl-Deposited Metal-Organic Framework NU-1000: Insights from First-Principles Calculations.

The hydrogenation of CO2 to high-value-added liquid fuels is crucial for greenhouse gas emission reduction and optimal utilization of carbon resources. Developing supported heterogeneous catalysts is a key strategy in this context, as they offer well-defined active sites for in-depth mechanistic studies and improved catalyst design. Here, we conducted extensive first-principles calculations to systematically explore the reaction mechanisms for CO2 hydrogenation on a heterogeneous bimetal NiAl-deposited metal-organic framework (MOF) NU-1000 and its catalytic performance as atomically dispersed catalysts for CO2 hydrogenation to formic acid (HCOOH), formaldehyde (H2CO), and methanol (CH3OH). The present results reveal that the presence of the NiAl-oxo cluster deposited on NU-1000 efficiently activates H2, and the facile heterolysis of H2 on Ni and adjacent O sites serves as a precursor to the hydrogenation of CO2 into various C1 products HCOOH, H2CO, and CH3OH. Generally, H2 activation is the rate-determining step in the entire CO2 hydrogenation process, the corresponding relatively low free energy barriers range from 14.5 to 15.9 kcal/mol, and the desorption of products on NiAl-deposited NU-1000 is relatively facile. Although the Al atom does not directly participate in the reaction, its presence provides exposed oxygen sites that facilitate the heterolytic cleavage of H2 and the hydrogenation of C1 intermediates, which plays an important role in enhancing the catalytic activity of the Ni site. The present study demonstrates that the catalytic performance of NU-1000 can be finely tuned by depositing heterometal-oxo clusters, and the porous MOF should be an attractive platform for the construction of atomically dispersed catalysts.