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      Ultrathin metal/covalent–organic framework membranes towards ultimate separation

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          Abstract

          Ultrathin 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.

          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.

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          Most cited references219

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          Maximizing the right stuff: The trade-off between membrane permeability and selectivity

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            Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites.

            The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.
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              Membranes. Metal-organic framework nanosheets as building blocks for molecular sieving membranes.

              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.
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                Author and article information

                Journal
                CSRVBR
                Chemical Society Reviews
                Chem. Soc. Rev.
                Royal Society of Chemistry (RSC)
                0306-0012
                1460-4744
                July 15 2019
                2019
                : 48
                : 14
                : 3811-3841
                Affiliations
                [1 ]MOE Key Laboratory of Macromolecular Synthesis and Functionalization
                [2 ]Department of Polymer Science and Engineering
                [3 ]Zhejiang University
                [4 ]Hangzhou 310027
                [5 ]China
                [6 ]Department of Mechanical Engineering
                [7 ]City University of Hong Kong
                [8 ]Hong Kong 999077
                Article
                10.1039/C9CS00322C
                31179451
                ff708a53-4f41-4198-bd64-4340da3d3382
                © 2019

                http://rsc.li/journals-terms-of-use

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