Search Results (59)

Developing highly permeable and selective membranes for energy-efficient CO₂/CH₄ separation remains challenging. Mixed-matrix membranes (MMMs) integrating polymer matrices with metal–organic frameworks (MOFs) offer significant potential. However, rational filler–matrix matching presents substantial difficulties, constraining separation performance. In this work, defects were engineered within fluorinated MOF ZU-61 through the partial replacement of 4,4′-bipyridine linkers with pyridine modulators, producing high-porosity HP-ZU-61 nanoparticles exhibiting a 267% BET surface area enhancement (992.9 m² g⁻¹) over low-porosity ZU-61 (LP-ZU-61) (372.2 m² g⁻¹). The HP-ZU-61/6FDA-DAM MMMs (30 wt.%) demonstrated homogeneous filler dispersion and pre-served crystallinity, achieving a CO₂ permeability of 1626 barrer and CO₂/CH₄ selectivity (33), surpassing the 2008 Robeson upper bound. Solution-diffusion modeling indicated ligand deficiencies generated accelerated diffusion pathways, while defect-induced unsaturated metal sites functioned as strong CO₂ adsorption centers that maintained solubility selectivity. This study establishes defect engineering in fluorinated MOF-based MMMs as a practical strategy to concurrently overcome the permeability–selectivity trade-off for efficient CO₂ capture. Full article

MOF-808 was synthesized using different (perfluoro)carboxylic acid modulators, including acetic acid (AA), butyric acid (BA), trifluoroacetic acid (TFAA) and heptafluorobutyric acid (HFBA). These samples were incorporated into co-polyimide 6FDA-DAM:DABA (6FDD), and the performance of the resulting MMMs was assessed for C₂ and C₃ olefin/paraffin separation. Enhanced permeability was observed for both C₂H₄/C₂H₆ and C₃H₆/C₃H₈ mixtures thanks to the introduced porosity upon filler incorporation in all cases. Due to the large pore size of MOF-808, diffusion-selective permeation through the polymer phase of the MMMs determined the eventual selectivity for C2 gases, leading to separation factors similar to that of the unfilled 6FDD membrane. For C₃H₆/C₃H₈ separation, the incorporation of fluorinated MOFs significantly improved separation performance, unlike their non-fluorinated counterparts. The unfilled 6FDD membrane exhibited a C₃H₆/C₃H₈ separation factor of 7.4 with a C₃H₆ permeability of 22 Barrer, while the incorporation of MOF-808-TFAA and MOF-808-HFBA led to C₃H₆/C₃H₈ separation factors of 13.1 and 13.5 with corresponding improved C₃H₆ permeabilities of 42 Barrer and 33 Barrer, respectively. Considering that these MMMs showed C₃H₆ permeabilities similar to those of MMMs containing their non-fluorinated MOF counterparts that exhibited no enhancement in membrane selectivity, the improved C₃H₆/C₃H₈ separation factor was attributed to the preferential adsorption of C₃H₈ over C3H6 on the fluorinated MOFs, acting as a trap for C₃H₈ and reducing its diffusivity. These results highlight the significance of matching the permeation characteristics of the selected polymer-filler pair on MMM performance for different gas pairs. Full article

Cu-BTC (HKUST-1) metal–organic framework (MOF) is widely recognized for its carbon capture capability due to its unsaturated copper sites, high surface area, and well-defined porous structure. This study developed mixed matrix membranes (MMMs) using cellulose triacetate (CTA), incorporating bimetallic Ni-Cu-BTC MOFs for CO₂/CH₄ separation, and benchmarked them against membranes fabricated with monometallic Cu-BTC. CTA was selected for its biodegradability, membrane-forming properties, and cost-effectiveness. The optimized membrane with 10 wt.% Ni-Cu-BTC achieved a CO₂ permeability of 22.9 Barrer at 25 °C and 5 bar—more than twice that of pristine CTA—with a CO₂/CH₄ selectivity of 33.8. This improvement stems from a 51.66% increase in fractional free volume, a 49.30% rise in the solubility coefficient, and a 51.94% boost in the diffusivity coefficient. Dual-sorption model analysis further confirmed enhanced solubility and adsorption mechanisms. These findings establish CTA/Ni-Cu-BTC membranes as promising candidates for high-performance CO₂ separation in natural gas purification and related industrial processes. Full article

Hybrid materials based on porous organic polymers (POPs) and metal–organic frameworks (MOFs) are increasing attention for advanced separation processes due to the possibility to combine their properties. POPs provide high surface areas, chemical stability, and tunable porosity, while MOFs contribute a high variety of defined crystalline structures and enhanced separation characteristics. The combination (or hybridization) with PIMs gives rise to mixed-matrix membranes (MMMs) with improved permeability, selectivity, and long-term stability. However, interfacial compatibility remains a key limitation, often addressed through polymer functionalization or controlled dispersion of the MOF phase. MOF/COF hybrids are more used as biochemical sensors with elevated sensitivity, catalytic applications, and wastewater remediation. They are also very well known in the gas sorption and separation field, due to their tunable porosity and high electrical conductivity, which also makes them feasible for energy storage applications. Last but not less important, hybrids with other POPs, such as hyper-crosslinked polymers (HCPs), covalent triazine frameworks (CTFs), or conjugated microporous polymers (CMPs), offer enhanced functionality. MOF/HCP hybrids combine ease of synthesis and chemical robustness with tunable porosity. MOF/CTF hybrids provide superior thermal and chemical stability under harsh conditions, while MOF/CMP hybrids introduce π-conjugation for enhanced conductivity and photocatalytic activity. These and other findings confirm the potential of MOF-POP hybrids as next-generation materials for gas separation and carbon capture applications. Full article

Membrane technology has been widely used in industrial CO₂ capturing, gas purification and gas separation, arousing attention due to its advantages of high efficiency, energy saving and environmental protection. In the context of reducing global carbon emissions and combating climate change, it is particularly important to capture and separate greenhouse gasses such as CO₂. Zr-MOF can be used as a multi-dimensional modification on the polymer membrane to prepare self-assembled MOF-based mixed matrix membranes (MMMs), aiming at the problem of weak adhesion or bonding force between the separation layer and the porous carrier. When defective UiO-66 is applied to PVDF membrane as a functional layer, the CO₂ separation performance of the PVDF membrane is significantly improved. TUT-UiO-3-TTN@PVDF has a CO₂ permeation flux of 14,294 GPU and a selectivity of 27 for CO₂/N₂ and 18 for CO₂/CH₄, respectively. The CO₂ permeability and selectivity of the membrane exhibited change after 40 h of continuous operation, significantly improving the gas separation performance and showing exceptional stability for large-scale applications. Full article

This paper introduces a pioneering approach that combines ex situ synthesis with advanced manufacturing to develop ZIF-67-PA12 Nylon composites with mixed-matrix membranes (MMMs), with the goal of enhancing hydrogen storage systems. One method involves producing MOF-PA12 composite powders through an in situ process, which is then commonly used as a base powder for powder bed fusion (PBF) to fabricate various structures. However, developing the in situ MOF-PA12 matrix presents challenges, including limited spreadability and processability at higher MOF contents, as well as reduced porosity due to pore blockage by polymers, ultimately diminishing hydrogen storage capacity. To overcome these issues, PBF is employed to form PA12 powder into films, followed by the ex situ direct synthesis of ZIF-67 onto these substrates at loadings exceeding those typically used in conventional MMM composites. In this study, ZIF-67 mass loadings ranging from 2 to 30 wt.% were synthesized on both PA12 powder and printed film substrates, with loadings on printed PA12 films extended up to 60 wt.%. ZIF-67-PA12-60(f) demonstrated a hydrogen capacity of 0.56 wt.% and achieved 1.53 wt.% for ZIF-67-PA12-30(p); in comparison, PA12 exhibited a capacity of 0.38 wt.%. This was undertaken to explore a range of ZIF-67 Metal–organic frameworks (MOFs) to assess their impact on the properties of the composite, particularly for hydrogen storage applications. Our results demonstrate that ex situ-synthesized ZIF-67-PA12 composite MMMs, which can be used as a final product for direct application and do not require the use of in situ pre-synthesized powder for the PBF process, not only retain significant hydrogen storage capacities, but also offer advantages in terms of repeatability, cost-efficiency, and ease of production. These findings highlight the potential of this innovative composite material as a practical and efficient solution for hydrogen storage, paving the way for advancements in energy storage technologies. Full article

The exploitation of high-performance membranes selective for propylene is important for developing energy-efficient propylene/propane (C₃H₆/C₃H₈) separation technologies. Although metal–organic frameworks with a molecular sieving property have been considered promising filler materials in mixed-matrix membranes (MMMs), their use in practical applications has been challenging due to a lack of interface compatibility. Herein, we adopted a surface coordination strategy that involved rationally utilizing carboxyl-functionalized PIM-1 (cPIM) and ZIF-8 to prepare a mixed-matrix membrane for efficient propylene/propane separation. The interfacial coordination between the polymer and the MOF improves their compatibility and eliminates the need for additional modification of the MOF, thereby maximizing the inherent screening performance of the MOF filler. Additionally, the utilization of porous PIM-1 guaranteed the high permeability of the MMMs. The obtained MMMs exhibited excellent separation performance. The 30 wt% ZIF-8/cPIM-1 membrane performed the best, exhibiting a high C₃H₆ permeability of 1023 Barrer with a moderate C₃H₆/C₃H₈ selectivity of 13.97 under 2 bars of pressure. This work presents a method that can feasibly be used for the preparation of defect-free MOF-based MMMs for specific gas separations. Full article

The selective separation of small molecules at the sub-nanometer scale has broad application prospects in the field, such as energy, catalysis, and separation. Conventional polymeric membrane materials (e.g., nanofiltration membranes) for sub-nanometer scale separations face challenges, such as inhomogeneous channel sizes and unstable pore structures. Combining polymers with metal–organic frameworks (MOFs), which possess uniform and intrinsic pore structures, may overcome this limitation. This combination has resulted in three distinct types of membranes: MOF polycrystalline membranes, mixed-matrix membranes (MMMs), and thin-film nanocomposite (TFN) membranes. However, their effectiveness is hindered by the limited regulation of the surface properties and growth of MOFs and their poor interfacial compatibility. The main issues in preparing MOF polycrystalline membranes are the uncontrollable growth of MOFs and the poor adhesion between MOFs and the substrate. Here, polymers could serve as a simple and precise tool for regulating the growth and surface functionalities of MOFs while enhancing their adhesion to the substrate. For MOF mixed-matrix membranes, the primary challenge is the poor interfacial compatibility between polymers and MOFs. Strategies for the mutual modification of MOFs and polymers to enhance their interfacial compatibility are introduced. For TFN membranes, the challenges include the difficulty in controlling the growth of the polymer selective layer and the performance limitations caused by the “trade-off” effect. MOFs can modulate the formation process of the polymer selective layer and establish transport channels within the polymer matrix to overcome the “trade-off” effect limitations. This review focuses on the mechanisms of synergistic construction of polymer–MOF membranes and their structure–nanofiltration performance relationships, which have not been sufficiently addressed in the past. Full article

As the atmospheric carbon dioxide (CO₂) concentration rapidly rises, carbon capture, utilization, and storage (CCUS) is an emerging field for climate change mitigation. Various carbon capture technologies are in development with the help of adsorbents, membranes, solvent-based systems, etc. One of the main challenges in this field is the removal of CO₂ from nitrogen (N₂) gas. This paper focuses on mixed matrix membrane technology, for which the CO₂/N₂ separation performance is based on differences in gas permeations. Membrane separation and purification technologies are widely studied for carbon capture. Microporous adsorbents such as zeolites and metal organic frameworks (MOFs) for carbon capture have been attracting researchers’ attention due to their highly porous structures, high selectivity values, and tunable porosities. Utilizing microporous adsorbents dispersed within a novel, blended polymer matrix, fourteen membranes were prepared with the commercial MOF ZIF-8, zeolite 13X, and kaolin, with methyl cellulose (MC) and polyvinyl alcohol (PVA), which were tested using a single gas permeation setup in this study. The addition of polyallylamine (PAH) as a chemisorbent was also investigated. These membranes were synthesized both with and without a polyacrylonitrile (PAN) support to compare their performances. MC was found to be an ideal polymeric matrix component to develop free-standing MMMs. At 24 °C and a relatively low feed pressure of 2.36 atm, a free-standing zeolite-13X-based membrane (MC/PAH/13X/PVA) exhibited the highest N₂/CO₂ selectivity of 2.8, with a very high N₂ permeability of 6.9 × 10⁷ Barrer. Upon the optimization of active layer thickness and filler weight percentages, this easily fabricated free-standing MMM made of readily available materials is a promising candidate for CO₂ purification through nitrogen removal. Full article

Metal–organic frameworks (MOFs) represent the largest class of materials among crystalline porous materials ever developed, and have attracted attention as core materials for separation technology. Their extremely uniform pore aperture and nearly unlimited structural and chemical characteristics have attracted great interest and promise for applying MOFs to adsorptive and membrane-based separations. This paper reviews the recent research into and development of MOF membranes for gas separation. Strategies for polycrystalline membranes and mixed-matrix membranes are discussed, with a focus on separation systems involving hydrocarbon separation, CO₂ capture, and H₂ purification. Challenges to and opportunities for the industrial deployment of MOF membranes are also discussed, providing guidance for the design and fabrication of future high-performance membranes. The contributions of the underlying mechanism to separation performance and adopted strategies and membrane-processing technologies for breaking the selectivity/permeability trade-off are discussed. Full article

Thin films of metal–organic frameworks (MOFs) on polymer substrates and MOF/polymer mixed-matrix membranes play crucial roles in advancing the field of gas separation membranes. In this paper, we present a novel method for the direct formation of continuous ZIF-8 crystal films on a polymer substrate doped with Zn²⁺. Our approach involves ion exchange between the doped zinc ions within the substrate and sodium ions in the presence of a CH₃COONa additive, as well as interfacial complexation with eluted zinc ions and 2-methylimidazole (2-MeIM). The key factors affecting the formation of ZIF-8 crystals on the substrate were the concentrations of CH₃COONa and 2-MeIM. A time-course analysis revealed that the nucleation rate during the early stages of the reaction significantly affected the surface morphology of the resulting ZIF-8 crystal films. Specifically, a higher nucleation rate led to the formation of continuous small ZIF-8 crystal films. This innovative approach enables the fabrication of densely packed, uniform ZIF-8 crystal films. Full article

MOF-74 (metal–organic framework) is utilized as a filler in mixed-matrix membranes (MMMs) to improve gas selectivity due to its unique one-dimensional hexagonal channels and high-density open metal sites (OMSs), which exhibit a strong affinity for CO₂ molecules. Reducing the agglomeration of nanoparticles and improving the compatibility with the matrix can effectively avoid the existence of non-selective voids to improve the gas separation efficiency. We propose a novel, layer-by-layer modification strategy for MOF-74 with graphene oxide. Two-dimensional graphene oxide nanosheets as a supporting skeleton creatively improve the dispersion uniformity of MOFs in MMMs, enhance their interfacial compatibility, and thus optimize the selective gas permeability. Additionally, they extended the gas diffusion paths, thereby augmenting the dissolution selectivity. Compared with doping with a single component, the use of a GO skeleton to disperse MOF-74 into Pebax^®1657 (Polyether Block Amide) achieved a significant improvement in terms of the gas separation effect. The CO₂/N₂ selectivity of Pebax^®1657-MOF-74 (Ni)@GO membrane with a filler concentration of 10 wt% was 76.96, 197.2% higher than the pristine commercial membrane Pebax^®1657. Our results highlight an effective way to improve the selective gas separation performance of MMMs by functionalizing the MOF supported by layered GO. As an efficient strategy for developing porous MOF-based gas separation membranes, this method holds particular promise for manufacturing advanced carbon dioxide separation membranes and also concentrates on improving CO₂ capture with new membrane technologies, a key step in reducing greenhouse gas emissions through carbon capture and storage. Full article

Carbon dioxide (CO₂), which results from fossil fuel combustion and industrial processes, accounts for a substantial part of the total anthropogenic greenhouse gases (GHGs). As a result, several carbon capture, utilization and storage (CCUS) technologies have been developed during the last decade. Chemical absorption, adsorption, cryogenic separation and membrane separation are the most widely used post-combustion CO₂ capture technologies. This study reviews post-combustion CO₂ capture technologies and the latest progress in membrane processes for CO₂ separation. More specifically, the objective of the present work is to present the state of the art of membrane-based technologies for CO₂ capture from flue gases and focuses mainly on recent advancements in commonly employed membrane materials. These materials are utilized for the fabrication and application of novel composite membranes or mixed-matrix membranes (MMMs), which present improved intrinsic and surface characteristics and, thus, can achieve high selectivity and permeability. Recent progress is described regarding the utilization of metal–organic frameworks (MOFs), carbon molecular sieves (CMSs), nanocomposite membranes, ionic liquid (IL)-based membranes and facilitated transport membranes (FTMs), which comprise MMMs. The most significant challenges and future prospects of implementing membrane technologies for CO₂ capture are also presented. Full article

The use of mixed matrix membranes (MMMs) comprising metal–organic frameworks (MOFs) for the separation of CO₂ from flue gas has gained recognition as an effective strategy for enhancing gas separation efficiency. When incorporating porous materials like MOFs into a polymeric matrix to create MMMs, the combined characteristics of each constituent typically manifest. Nevertheless, the inadequate dispersion of an inorganic MOF filler within an organic polymer matrix can compromise the compatibility between the filler and matrix. In this context, the aspiration is to develop an MMM that not only exhibits optimal interfacial compatibility between the polymer and filler but also delivers superior gas separation performance, specifically in the efficient extraction of CO₂ from flue gas. In this study, we introduce a modification technique involving the grafting of poly(ethylene glycol) diglycidyl ether (PEGDE) onto a UiO-66-NH₂ MOF filler (referred to as PEG-MOF), aimed at enhancing its compatibility with the 6FDA-durene matrix. Moreover, the inherent CO₂-philic nature of PEGDE is anticipated to enhance the selectivity of CO₂ over N₂ and CH₄. The resultant MMM, incorporating 10 wt% of PEG-MOF loading, exhibits a CO₂ permeability of 1671.00 Barrer and a CO₂/CH₄ selectivity of 22.40. Notably, these values surpass the upper bound reported by Robeson in 2008. Full article

Mixed matrix membranes (MMMs) have shown great potential in pervaporation (PV). As for many novel membrane materials however, lab-scale testing often involves synthetic feed solutions composed of mixed pure components, overlooking the possibly complex interactions and effects caused by the numerous other components in a real PV feed. This work studies the performance of MMMs with two different types of fillers, a core-shell material consisting of ZIF-8 coated on mesoporous silica and a hollow sphere of silicalite-1, in the PV of a real fermented wheat/hay straw hydrolysate broth for the production of bio-ethanol. All membranes, including a reference unfilled PDMS, show a declining permeability over time. Interestingly, the unfilled PDMS membrane maintains a stable separation factor, whereas the filled PDMS membranes rapidly lose selectivity to levels below that of the reference PDMS membrane. A membrane autopsy using XRD and SEM-EDX revealed an almost complete degradation of the crystalline ZIF-8 in the MMMs. Reference experiments with ZIF-8 nanoparticles in the fermentation broth demonstrated the influence of the broth on the ZIF-8 particles. However, the observed effects from the membrane autopsy could not exactly be replicated, likely due to distinct differences in conditions between the in-situ pervaporation process and the ex-situ reference experiments. These findings raise significant questions regarding the potential applicability of MOF-filled MMMs in real-feed pervaporation processes and, potentially, in harsh condition membrane separations in general. This study clearly confirms the importance of testing membranes in realistic conditions. Full article