Ultrathin metal-organic framework membrane production by gel-vapour deposition.
TL;DR: A gel–vapour deposition strategy is used to fabricate composite membranes with less than 20 nm thicknesses and high gas permeances and selectivities, and the in situ scale-up processing of a MOF membrane module is demonstrated without deterioration in selectivity.
Abstract: Ultrathin, molecular sieving membranes composed of microporous materials offer great potential to realize high permeances and selectivities in separation applications, but strategies for their production have remained a challenge. Here we show a route for the scalable production of nanometre-thick metal–organic framework (MOF) molecular sieving membranes, specifically via gel–vapour deposition, which combines sol–gel coating with vapour deposition for solvent-/modification-free and precursor-/time-saving synthesis. The uniform MOF membranes thus prepared have controllable thicknesses, down to ~17 nm, and show one to three orders of magnitude higher gas permeances than those of conventional membranes, up to 215.4 × 10−7 mol m−2 s−1 Pa−1 for H2, and H2/C3H8, CO2/C3H8 and C3H6/C3H8 selectivities of as high as 3,400, 1,030 and 70, respectively. We further demonstrate the in situ scale-up processing of a MOF membrane module (30 polymeric hollow fibres with membrane area of 340 cm2) without deterioration in selectivity. MOF-based membranes have shown great promise in separation applications, but producing thin membranes that allow for high fluxes remains challenging. Here, the authors use a gel–vapour deposition strategy to fabricate composite membranes with less than 20 nm thicknesses and high gas permeances and selectivities.
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TL;DR: This comprehensive review discusses opportunities and challenges related to the formation of pure MOF films and mixed-matrix membranes and introduces a simple membrane performance score that has been tabulated for all of the literature data compiled in this review.
Abstract: Metal-organic frameworks (MOFs) represent the largest known class of porous crystalline materials ever synthesized Their narrow pore windows and nearly unlimited structural and chemical features have made these materials of significant interest for membrane-based gas separations In this comprehensive review, we discuss opportunities and challenges related to the formation of pure MOF films and mixed-matrix membranes (MMMs) Common and emerging separation applications are identified, and membrane transport theory for MOFs is described and contextualized relative to the governing principles that describe transport in polymers Additionally, cross-cutting research opportunities using advanced metrologies and computational techniques are reviewed To quantify membrane performance, we introduce a simple membrane performance score that has been tabulated for all of the literature data compiled in this review These data are reported on upper bound plots, revealing classes of MOF materials that consistently demonstrate promising separation performance Recommendations are provided with the intent of identifying the most promising materials and directions for the field in terms of fundamental science and eventual deployment of MOF materials for commercial membrane-based gas separations
575 citations
TL;DR: In this article, the fabrication of ZIF nanocomposite membranes by means of an all-vapor-phase processing method based on atomic layer deposition (ALD) of ZnO in a porous support followed by ligand vapor treatment was demonstrated.
Abstract: Zeolitic imidazolate framework (ZIF) membranes are emerging as a promising energy-efficient separation technology However, their reliable and scalable manufacturing remains a challenge We demonstrate the fabrication of ZIF nanocomposite membranes by means of an all-vapor-phase processing method based on atomic layer deposition (ALD) of ZnO in a porous support followed by ligand-vapor treatment After ALD, the obtained nanocomposite exhibits low flux and is not selective, whereas after ligand-vapor (2-methylimidazole) treatment, it is partially transformed to ZIF and shows stable performance with high mixture separation factor for propylene over propane (an energy-intensive high-volume separation) and high propylene flux Membrane synthesis through ligand-induced permselectivation of a nonselective and impermeable deposit is shown to be simple and highly reproducible and holds promise for scalability
281 citations
TL;DR: This review on the deep understanding of MOF coatings will bring better directions into the rational design of high-performance MOF-based materials and open up new opportunities for MOF applications.
Abstract: Metal–organic frameworks (MOFs) as a new kind of porous crystalline materials have attracted much interest in many applications due to their high porosity, diverse structures, and controllable chemical structures. However, the specific geometrical morphologies, limited functions and unsatisfactory performances of pure MOFs hinder their further applications. In recent years, an efficient approach to synthesize new composites to overcome the above issues has been achieved, by integrating MOF coatings with other functional materials, which have synergistic advantages in many potential applications, including batteries, supercapacitors, catalysis, gas storage and separation, sensors, drug delivery/cytoprotection and so on. Nevertheless, the systemic synthesis strategies and the relationships between their structures and application performances have not been reviewed comprehensively yet. This review emphasizes the recent advances in versatile synthesis strategies and broad applications of MOF coatings. A comprehensive discussion of the fundamental chemistry, classifications and functions of MOF coatings is provided first. Next, by modulating the different states (e.g. solid, liquid, and gas) of metal ion sources and organic ligands, the synthesis methods for MOF coatings on functional materials are systematically summarized. Then, many potential applications of MOF coatings are highlighted and their structure–property correlations are discussed. Finally, the opportunities and challenges for the future research of MOF coatings are proposed. This review on the deep understanding of MOF coatings will bring better directions into the rational design of high-performance MOF-based materials and open up new opportunities for MOF applications.
277 citations
TL;DR: This critical review presents the recent progress in metal-organic frameworks (MOFs) and related membranes (e.g., continuous MOF membranes and mixed-matrix membranes) for hydrocarbon separation and summarizes the potential barriers that exist from the academic to the ultimate industrial implementations and the prospects of future development.
Abstract: Hydrocarbon separation is one of the most critically important and complex industrial separation processes, offering versatile bulk chemicals and vital support to the national economy. Traditional separation technologies, such as cryogenic distillation and solvent extraction, are energy-intensive and cause serious environmental stress. Moreover, the growth of industries and technologies and the greater requirements for products (e.g., purity) lead to challenges that cannot be met using traditional separation methods. Adsorptive and membrane-based separations are recognized as energy-efficient alternatives by which to revolutionize the current energy-intensive conditions and satisfy the new demands. This critical review presents the recent progress in metal-organic frameworks (MOFs) and related membranes (e.g., continuous MOF membranes and mixed-matrix membranes) for hydrocarbon separation. The contributions of the underlying separation mechanisms (e.g., enthalpy-driven thermodynamic equilibrium, molecular sieving, kinetic separation based on molecular size, and combined mechanisms) and the adopted strategies (e.g., defect and microstructure control, membrane thickness and interfacial compatibility) to the breaking of trade-off (e.g., permeability/selectivity and capacity/selectivity) and the design of novel materials and processing technologies are discussed. Moreover, this review also summarizes the potential barriers that exist from the academic to the ultimate industrial implementations and the prospects of future development.
275 citations
TL;DR: The advanced strategies in fabricating ultrathin defect-free MOF/COF membranes such as in situ growth, contra-diffusion method, layer-by-layer (LBL) assembly, metal-based precursor as the pre-functionalized layer, interface-assisted strategy, and laminated assembly of MOF-COF nanosheets are presented.
Abstract: Metal/covalent–organic framework (MOF/COF) membranes have attracted increasing research interest and have been considered as state-of-the-art platforms applied in various environment- and energy-related separation/transportation processes. To break the trade-off between permeability and selectivity to achieve ultimate separation, recent studies have been oriented towards how to design and exploit ultrathin MOF/COF membranes (i.e. sub-1 μm-thick). Given great advances made in the past five years, it is valuable to timely and systematically summarize the recent development and shed light on the future trend in this multidisciplinary field. In this review, we first present the advanced strategies in fabricating ultrathin defect-free MOF/COF membranes such as in situ growth, contra-diffusion method, layer-by-layer (LBL) assembly, metal-based precursor as the pre-functionalized layer, interface-assisted strategy, and laminated assembly of MOF/COF nanosheets. Then, the recent progress in some emerging applications of ultrathin MOF/COF membranes beyond gas separation is highlighted, including water treatment and seawater desalination, organic solvent nanofiltration, and energy-related separation/transportation (i.e. lithium ion separation and proton conductivity). Finally, some unsolved scientific and technical challenges associated with future perspectives in this field are discussed, inspiring the development of next-generation separation membranes.
271 citations
References
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TL;DR: Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvents.
Abstract: Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m 2 /g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.
5,512 citations
TL;DR: The empirical upper bound relationship for membrane separation of gases initially published in 1991 has been reviewed with the myriad of data now presently available as mentioned in this paper, which indicates a different solubility selectivity relationship for perfluorinated polymers compared to hydrocarbon/aromatic polymers.
4,525 citations
TL;DR: Members of a selection of zeolitic imidazolate frameworks have high thermal stability and chemical stability in refluxing organic and aqueous media, and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2.
Abstract: A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390°C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO 2 capture from CO 2 /CO mixtures and extraordinary capacity for storing CO 2 : 1 liter of ZIF-69 can hold ∼83 liters of CO 2 at 273 kelvin under ambient pressure.
3,227 citations
1,457 citations
TL;DR: The preparation of 1-nanometer-thick sheets with large lateral area and high crystallinity from layered MOFs used as building blocks for ultrathin molecular sieve membranes, which achieve hydrogen gas permeance of up to several thousand gas permeation units (GPUs) with H2/CO2 selectivity greater than 200.
Abstract: Layered metal-organic frameworks would be a diverse source of crystalline sheets with nanometer thickness for molecular sieving if they could be exfoliated, but there is a challenge in retaining the morphological and structural integrity. We report the preparation of 1-nanometer-thick sheets with large lateral area and high crystallinity from layered MOFs. They are used as building blocks for ultrathin molecular sieve membranes, which achieve hydrogen gas (H2) permeance of up to several thousand gas permeation units (GPUs) with H2/CO2 selectivity greater than 200. We found an unusual proportional relationship between H2 permeance and H2 selectivity for the membranes, and achieved a simultaneous increase in both permeance and selectivity by suppressing lamellar stacking of the nanosheets.
1,312 citations