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Synthesis of ZIF-11 Membranes: The Influence of Preparation Technique and Support Type.

ABSTRACT: Due to its structural features, ZIF-11 is one of the most interesting materials for gas separation applications. Herein, we report a systematic study on the synthesis of ZIF-11 as a supported membrane. For this, we adapted optimized conditions for the ZIF-11 powder synthesis, identified in our previous works, to form ZIF layers on symmetric and asymmetric stainless-steel and asymmetric α-Al₂O₃ supports. Different techniques were investigated for the challenging layer formation, namely, in situ crystallization (ISC), multiple in situ crystallization (MISC), and the seeding and secondary growth (SSG) method. It was possible to deposit ZIF-11 on different supports by ISC and MISC, although it was difficult to obtain complete layers. SSG, in turn, was more effective in forming dense and well-intergrown ZIF-11 layers. This agrees well with the generally accepted fact that seeding considerably facilitates layer formation. Systematic studies of both individual steps of SSG (seeding and secondary growth) led to a basic understanding of layer formation of ZIF-11 on the different supports. The best membranes prepared by rub seeding and secondary growth achieved Knudsen selectivity. Improved gas separation performance is expected if the formation of defects can be avoided.

SUBMITTER: Reif B

PROVIDER: S-EPMC8303830 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Relationship between Ethane and Ethylene Diffusion inside ZIF-11 Crystals Confined in Polymers to Form Mixed-Matrix Membranes.

Project description:Self-diffusivities of ethane were measured by multinuclear pulsed field gradient (PFG) NMR inside zeolitic imidazolate framework-11 (ZIF-11) crystals dispersed in several selected polymers to form mixed-matrix membranes (MMMs). These diffusivities were compared with the corresponding intracrystalline self-diffusivities in ZIF-11 crystal beds. It was observed that the confinement of ZIF-11 crystals in ZIF-11 / Torlon MMM can lead to a decrease in the ethane intracrystalline self-diffusivity. Such diffusivity decrease was observed at different temperatures used in this work. PFG NMR measurements of the temperature dependence of the intracrystalline self-diffusivity of ethylene in the same ZIF-11 / Torlon MMM revealed similar diffusivity decrease as well as an increase in the diffusion activation energy in comparison to those in unconfined ZIF-11 crystals in a crystal bed. These observations for ethane and ethylene were attributed to the reduction of the flexibility of the ZIF-11 framework due to the confinement in Torlon leading to a smaller effective aperture size of ZIF-11 crystals. Surprisingly, the intra-ZIF diffusion selectivity for ethane and ethylene was not changed appreciably by the confinement of ZIF-11 crystals in Torlon in comparison to the selectivity in a bed of ZIF-11 crystals. No ZIF-11 confinement effects leading to a reduction in the intracrystalline self-diffusivity of ethane and ethylene were observed for the other two studied MMM systems: ZIF-11 / Matrimid and ZIF-11 / 6FDA-DAM. The absence of the confinement effect in the latter MMMs can be related to the lower values of the polymer bulk modulus in these MMMs in comparison to that in ZIF-11 / Torlon MMM. In addition, there may be a contribution from possible differences in the ZIF-11/polymer adhesion in different MMM types.

| S-EPMC7449132 | biostudies-literature

Influence of Substitutional Defects in ZIF-8 Membranes on Reverse Osmosis Desalination: A Molecular Dynamics Study.

Project description:In this study, molecular dynamics simulation is used to investigate the effects of water-based substitutional defects in zeolitic imidazolate frameworks (ZIF)-8 membranes on their reverse osmosis (RO) desalination performance. ZIF-8 unit cells containing up to three defect sites are used to construct the membranes. These substitutional defects can either be Zn defects or linker defects. The RO desalination performance of the membranes is assessed in terms of the water flux and ion rejection rate. The effects of defects on the interactions between the ZIF-8 membranes and NaCl are investigated and explained with respect to the radial distribution function (RDF) and ion density distribution. The results show that ion adsorption on the membranes occurs at either the nitrogen atoms or the defect sites. Complete NaCl rejection can be achieved by introducing defects to change the size of the pores. It has also been discovered that the presence of linker defects increases membrane hydrophilicity. Overall, molecular dynamics simulations have been used in this study to show that water-based substitutional defects in a ZIF-8 structure reduce the water flux and influence its hydrophilicity and ion adsorption performance, which is useful in predicting the type and number of defect sites per unit cell required for RO applications. Of the seven ZIF-8 structures tested, pristine ZIF-8 exhibits the best RO desalination performance.

| S-EPMC8200035 | biostudies-literature

Aqueous-System-Enabled Spray-Drying Technique for the Synthesis of Hollow Polycrystalline ZIF-8 MOF Particles.

Project description:Zeolitic imidazolate framework-8 shares the same topology with sodalite zeolite but consists of Zn nodes bridged by imidazolate linkers to form a neutral open-framework structure. ZIF-8 has been recognized as a unique molecular sieving material with a flexible framework enabling interesting "gate-opening" functionality. Controlling the crystal size and shape is crucial for regulating the structural flexibilities and mass transport properties. The present study demonstrates that an aqueous-system-enabled spray-drying process enables the shape engineering of ZIF-8 with a hollow polycrystalline structure. It is notable that our synthesis route produces an amorphous zinc complex compound, which possesses a continuous random network partially with crystalline fillers, after spray drying followed by an amorphous-to-crystal transition via activation treatment using polar organic solvents. The size of primary ZIF-8 crystals consisting of secondary polycrystals depends on the kind of the organic solvent. The macro-/microscopic structures of hollow polycrystalline ZIF-8 significantly structurally enhanced the adsorption capacity and uptake rate. The large-scale, rapid production and enhanced adsorption performances make this continuous method a very promising candidate for industrial applications and shaping of MOF.

| S-EPMC6644740 | biostudies-literature

Efficient Separation of Acetylene-Containing Mixtures Using ZIF-8 Membranes.

Project description:Metal-organic framework (MOF) membranes show great potential in the separation of acetylene mixtures. In this work, we have prepared ZIF-8 membranes on polyamide (PA) substrates for the highly selective separation of acetylene/methane and acetylene/carbon dioxide mixtures. The C2H2/CH4 and C2H2/CO2 mixtures can be successfully separated using the ZIF-8 membranes, with separation factors of 12.1 and 1.8, respectively. Based on the results of the cross-permeation tests of C2H2/CH4, CO2/CH4, and C2H2/CO2, the separation mechanism of C2H2/CH4 in our ZIF-8 membrane can be attributed to a higher affinity for acetylene and molecular sieving effect, while C2H2/CO2 separation is related to thermodynamic factors. It is worth noting that this is the first example of MOF membranes to successfully separate C2H2 from CH4 and CO2.

| S-EPMC8655891 | biostudies-literature

Mo@ZIF-8 nanozyme preparation and its antibacterial property evaluation.

Project description:Types of nanozymes can produce free radicals and/or reactive oxygen species (ROS) to serve as broad spectrum antibacterial materials. Developing nanozyme-based antibacterial materials with good biocompatibility exhibits promising application prospects. In this study, we doped Mo to ZIF-8 (both components have good biocompatibility) to prepare a new nanozyme, Mo@ZIF-8, which can produce hydroxyl radicals (•OH) triggered by a low dosage of hydrogen peroxide (H2O2), exhibiting effective antibacterial capability against both Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus). This work provides a reference for the design of antibacterial nanozymes with good biocompatibility.

| S-EPMC9730516 | biostudies-literature

Influence of support-layer deformation on the intrinsic resistance of thin film composite membranes.

Project description:It is commonly believed that the overall permeation resistance of thin film composite (TFC) membranes is dictated by the crosslinked, ultrathin polyamide barrier layer, while the porous support merely serves as the mechanical support. Although this assumption might be the case under low transmembrane pressure, it becomes questionable under high transmembrane pressure. A highly porous support normally yields under a pressure of a few MPa, which can result in a significant level of compressive strain that may significantly increase the resistance to permeation. However, quantifying the influence of porous support deformation on the overall resistance of the TFC membrane is challenging. In particular, it is difficult to determine the deformation/strain of the membrane during active separation. In this study, we use nanoimprint lithography (NIL) to achieve precise compressive deformation in commercial TFC membranes. By adjusting the NIL conditions, membranes were compressed to strain levels up to 60%. SEM and AFM measurements showed that the compression had minimal impact on the barrier-layer surface morphology and total surface area with most of the deformation occurring in the support layer. DI water permeation measurements revealed that the water flux reduction decreases with an increase of strain level. Most significantly, the intrinsic membrane resistance showed negligible changes at strain levels lower than 30%-40%, but increased exponentially at higher strain levels, reaching 250%-500% of pristine (unstrained) membrane values. Using a resistance-in-series model, the strain dependency of the TFC membrane resistance can be described.

| S-EPMC6459622 | biostudies-literature

MYO10-filopodia support basement membranes at pre-invasive tumor boundaries

Project description:Myosin-X -silenced and control-silenced subcutaneous breast tumor xenografts in female NOD.scid mice

2022-09-27 | GSE166898 | GEO

High-aspect ratio zeolitic imidazolate framework (ZIF) nanoplates for hydrocarbon separation membranes.

Project description:Metal-organic frameworks with high aspect ratios have the potential to yield high-performance gas separation membranes. We demonstrate the scalable synthesis of high–aspect ratio zeolitic imidazolate framework (ZIF)–8 nanoplates via a direct template conversion method in which high aspect ratio–layered Zn hydroxide sheets [Zn5(NO3)2(OH)8] were used as the sacrificial precursor. Successful phase conversion occurs as a result of the collaboration of low template stability and delayed delivery of 2-methylimidazole in weakly interacting solvents, particularly using acetone. When the ZIF-8 nanoplates with an average aspect ratio of 20 were shear aligned in the 6FDA-DAM polymer matrix by bar coating, the separation performance for propylene/propane far surpassed that of the previously reported mixed matrix and polymeric membranes, showing a propylene permeability of 164 Barrer and selectivity of 33.4 at 40 weight % loadings.

| S-EPMC8730619 | biostudies-literature

High Performance of PIM-1/ZIF-8 Composite Membranes for O2/N2 Separation.

Project description:This work reports the preparation, characterization, and O2/N2 separation properties of composite membranes based on the polymer of intrinsic microporosity (PIM-1) and the zeolitic imidazolate framework (ZIF-8). Especially, the composite membranes were prepared by growing ZIF-8 nanoparticles on one side of the PIM-1 membrane in methanol. Fourier transform infrared spectroscopy and thermo-gravimetric analysis indicated that there is no strong chemical interaction between ZIF-8 nanoparticles and PIM-1 chains. Scanning electron microscopy images showed that ZIF-8 nanoparticles adhere well to the PIM-1 membrane surface. The pure-gas permeation results confirmed that growth of ZIF-8 on the PIM-1 membrane can enhance the performance of O2/N2 separation. Particularly, the O2/N2 separation performance of the PIM-1/ZIF-8-7 composite membrane exceeds the Robeson upper bound line.

| S-EPMC6788045 | biostudies-literature

Cross-Linked Polyimide/ZIF-8 Mixed-Matrix Membranes by In Situ Formation of ZIF-8: Effect of Cross-Linking on Their Propylene/Propane Separation.

Project description:Despite their potential for the scalable production of mixed-matrix membranes (MMMs), the MMMs prepared by the polymer-modification-enabled in situ metal-organic framework formation (PMMOF) process showed a considerable reduction in gas permeability as the filler loading increased. It was hypothesized that a correlation existed between the decrease in permeability and the change in the properties of the polymer, such as free volume and chain flexibility, upon in situ MOF formation. Herein, we aim to address the permeability reduction by using a cross-linked polyimide (6FDA-DAM:DABA (3:2)). It was found the degree of cross-linking affected not only the properties of the polymer, but also the in situ formation of the ZIF-8 filler particles in the cross-linked polymer. The proper degree of cross-linking resulted in suppressing C3H6 permeability reduction, suggesting a possible strategy to overcome the issue of PMMOF. The swelling of the polymer followed by chain rearrangement during the PMMOF, as well as the structural rigidity of the polymer, were found to be critical in mitigating permeability reduction.

| S-EPMC9609502 | biostudies-literature

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