Metal–organic frameworks (MOFs)
are inherently crystalline,
brittle porous solids. Conversely, polymers are flexible, malleable,
and processable solids that are used for a broad range of commonly
used technologies. The stark differences between the nature of MOFs
and polymers has motivated efforts to hybridize crystalline MOFs and
flexible polymers to produce composites that retain the desired properties
of these disparate materials. Importantly, studies have shown that
MOFs can be used to influence polymer structure, and polymers can
be used to modulate MOF growth and characteristics. In this Review,
we highlight the development and recent advances in the synthesis
of MOF-polymer mixed-matrix membranes (MMMs) and applications of these
MMMs in gas and liquid separations and purifications, including aqueous
applications such as dye removal, toxic heavy metal sequestration,
and desalination. Other elegant ways of synthesizing MOF-polymer hybrid
materials, such as grafting polymers to and from MOFs, polymerization
of polymers within MOFs, using polymers to template MOFs, and the
bottom-up synthesis of polyMOFs and polyMOPs are also discussed. This
review highlights recent papers in the advancement of MOF-polymer
hybrid materials, as well as seminal reports that significantly advanced
the field.
We report the first self-assembled porous monolayer and free-standing multilayer films composed of metal−organic framework (MOF) nanoparticles. Selfassembled MOF monolayers (SAMMs) were assembled at a liquid−air interface to produce films that are 87 wt % (89 vol %) MOF. Monolayer self-assembly was aided by growing a layer of poly(methyl methacrylate) (PMMA) on the particle surface using a histamine anchor. SAMMs could be stacked to obtain MOF multilayers, including alternating MOF/polymer heterostructures. SAMMs were coated on silicon microparticles, and a MOF film constructed of only five stacked layers could be manipulated as a free-standing, opalescent film. These monolayers are a significant advancement for obtaining highly functional porous membranes and coatings.
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