Postsynthetic Polymerization Research Articles

Preparation of Superhydrophobic Metal–Organic Framework/Polymer Composites as Stable and Efficient Catalysts

Metal-organic frameworks (MOFs), as a chemical platform, combined with multifunctional polymers are of interest in catalytic applications, which can not only inherit the outstanding properties of the two components but also lead to unique synergistic effects. Nonetheless, most MOFs possess varying degrees of water instability, which limits their real application. Herein, we fabricated highly hydrophobic MOF/polymer composites via a universal post-synthetic polymerization strategy as efficient catalysts. Polyaniline (PANI) was first hybridized with MOFs by vapor deposition polymerization, and then, hydrophobic molecules were grafted to the PANI by a covalent linking process, thereby forming a superhydrophobic MOF/PANI hybrid material (MOF/PANI-shp). The resultant MOF/PANI-shp not only obtains superior moisture/water resistance without significantly disturbing the original features but also exhibits a novel catalytic selectivity in styrene oxidation because of the accessible sites and synergistic effects. Such a synthetic strategy for the MOF/polymer catalyst opens a new avenue for the design of a unique catalyst with outstanding catalytic efficiency, selectivity, and stability.

Eu3+ functionalized robust membranes based on the post-synthetic copolymerization of a metal-organic framework and ethyl methacrylate.

Metal-organic frameworks (MOFs) are recognized as a class of promising crystalline materials. However, their subsequent processing and shaping still remain a challenge, and one emerging strategy is to hybridize MOFs with flexible polymers. Herein, by utilizing a simple and cost-effective post-synthetic polymerization method, under mild conditions, MOF particles with olefin bonds are covalently linked to polymer chains. Moreover, photoactive europium ions are also introduced into this system during the polymerization process. Importantly, the resulting MOF-based membrane (MOF1-Eu3+@PEMA) is uniform, showing great structural and fluorescence stability against strict conditions (aqueous solutions with pH 0.98-13.11). Besides, given its good luminescence properties, the membrane is employed for the identification of common volatile organic compounds and a selective response to toluene was achieved. This work accelerates the practical applications of MOF-based membranes and enriches the methods for MOF modification.

Spray-Coating of Catalytically Active MOF-Polythiourea through Postsynthetic Polymerization.

A UiO-66-NCS MOF was formed by postsynthetic modification of UiO-66-NH2 . The UiO-66-NCS MOFs displays a circa 20-fold increase in activity against the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) compared to UiO-66-NH2 , making it the most active MOF materials using a validated high-throughput screening. The -NCS functional groups provide reactive handles for postsynthetic polymerization of the MOFs into functional materials. These MOFs can be tethered to amine-terminated polypropylene polymers (Jeffamines) through a facile room-temperature synthesis with no byproducts. The MOFs are then crosslinked into a MOF-polythiourea (MOF-PTU) composite material, maintaining the catalytic properties of the MOF and the flexibility of the polymer. This MOF-PTU hybrid material was spray-coated onto Nyco textile fibers, displaying excellent adhesion to the fiber surface. The spray-coated fibers were screened for the degradation of DMNP and showed durable catalytic reactivity.

Spray‐Coating of Catalytically Active MOF–Polythiourea through Postsynthetic Polymerization

AbstractA UiO‐66‐NCS MOF was formed by postsynthetic modification of UiO‐66‐NH2. The UiO‐66‐NCS MOFs displays a circa 20‐fold increase in activity against the chemical warfare agent simulant dimethyl‐4‐nitrophenyl phosphate (DMNP) compared to UiO‐66‐NH2, making it the most active MOF materials using a validated high‐throughput screening. The −NCS functional groups provide reactive handles for postsynthetic polymerization of the MOFs into functional materials. These MOFs can be tethered to amine‐terminated polypropylene polymers (Jeffamines) through a facile room‐temperature synthesis with no byproducts. The MOFs are then crosslinked into a MOF–polythiourea (MOF–PTU) composite material, maintaining the catalytic properties of the MOF and the flexibility of the polymer. This MOF–PTU hybrid material was spray‐coated onto Nyco textile fibers, displaying excellent adhesion to the fiber surface. The spray‐coated fibers were screened for the degradation of DMNP and showed durable catalytic reactivity.

Novel Elastically Stretchable Metal-Organic Framework Laden Hydrogel with Pearl-Net Microstructure and Freezing Resistance through Post-Synthetic Polymerization.

Nanocomposite hydrogels (NCs) with mechanical properties suitable for a diverse range of applications can be made by combining polymer hydrogel networks with various inorganic nanoparticles. However, the mechanical properties and functions of conventional NCs are seriously limited by the poor structural or functional tunability of common nanofillers and by the low amounts of such fillers that can be added. Here, the fabrication of novel elastically stretchable and compressible nanocomposite hydrogels (MIL-101-MAAm/PAAm) with a distinctive pearl-net microstructure and a metal-organic framework (MOF) content in the range of 20-60 wt% through post-synthetic polymerization (PSP) is reported. The MOFs, which are compatible with polymers and have a high degree of modifiability in structure and functions, are used as nanofillers. Such MOF-laden hydrogels can withstand 500% tensile strain or 90% compressive strain without fracture and recover quickly upon unloading. They are also resistant to freezing at -25 °C. In addition, the problems associated with poor flexibility and processability of MOFs are overcome by the hybridization of hydrogel polymer matrices with MOFs. The results of this work not only provide a new perspective on preparing NCs but also indicate a promising path for applying MOFs in flexible devices.

Metal-Organic Framework Films and Their Potential Applications in Environmental Pollution Control.

Metal-organic frameworks (MOFs), an emerging class of porous hybrid inorganic-organic crystals, exhibit very important application prospects in gas storage and separation, heterogeneous catalysis, sensing, drug release, environmental decontamination, etc., due to their competitive advantages over other traditional porous materials (e.g., activated carbon and zeolite), including high surface areas, adjustable pore size, uniformly distributed metal centers, and tunable functionalities. However, MOF particles are usually difficult to be processed into application-specific devices because of their brittleness, insolubility, difficulty in molding, and low compatibility with other materials. It is an urgent need to shape MOF nanocrystals into various useful configurations by developing effective fabrication methods. Specifically, versatile functional MOF films with robustness and operation flexibility are highly desired. Although an increasing number of MOF films and their diverse applications have been demonstrated, this field is still at an emerging stage with challenging issues. In this Account, we describe our recent research progress on controllable synthesis of MOF films, highlighting postsynthetic polymerization, in situ interweaving, and solvent-free hot-pressing methods. Basically, two main synthesis concepts are involved, including incorporation of the performed MOF particles into polymer matrix and in situ growth of MOF coatings on surface. In MOF/polymer hybrid films, MOF nanocrystals were covalently linked by flexible polymer chains via graft copolymerization, interconnected by functional polymer chains via in situ polymerization, or adhered to polymer matrix via specific interactions at interface, consequently leading to a molecular-level homogeneous membrane or functional coating layer or foam. In these examples, the existence of polymer endows MOF films with favorable features of processability and flexibility, along with new functions. Moreover, we developed an in situ solvent-free hot-pressing method as a general approach for efficient fabrication of MOF coatings on various commercial substrates (e.g., cloth and metal foils), where metal ions or ligands were chemically bonded to the surface functional groups or metal sites at the early stage of nucleation and subsequently assembled into continuous, uniform, and stable MOF layers under confined conditions. We further extended it to a scalable manufacturing method, roll-to-roll production. MOF films severing as filters (MOFilters) have significant applications in air and water purification. They show high and stable performance in PM capture along with a low pressure drop, holding promise of application in both industrial and residential environments. Moreover, MOFilters can remove SO2 and O3 from air by adsorption and catalytic decomposition, respectively. Given the functional diversity of MOFs, mixed pollutants in solution could also be efficiently trapped by multifunctional MOF hollow tubes. We believe this Account will offer new insights for design and preparation of functional MOF films and coatings and accelerate the practical applications of MOFs.

Nylon-MOF Composites through Postsynthetic Polymerization.

Hybridization of metal-organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF-polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench-top approach to covalently tethered nylon-MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO-66-NH2 MOF with a growing polyamide fiber (PA-66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl-4-nitrophenyl phosphate, DMNP) compared to MOFs that are non-covalently, physically entrapped in nylon, thus highlighting the importance of MOF-polymer hybridization.

Nylon–MOF Composites through Postsynthetic Polymerization

AbstractHybridization of metal–organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF–polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench‐top approach to covalently tethered nylon–MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO‐66‐NH2 MOF with a growing polyamide fiber (PA‐66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl‐4‐nitrophenyl phosphate, DMNP) compared to MOFs that are non‐covalently, physically entrapped in nylon, thus highlighting the importance of MOF–polymer hybridization.

A new post-synthetic polymerization strategy makes metal-organic frameworks more stable.

Metal-organic frameworks are of interest in a number of host-guest applications. However, their weak coordination bonding often leads to instability in aqueous environments, particularly at extreme pH, and hence, is a challenging topic in the field. In this work, a two-step, post-synthetic polymerization method is used to create a series of highly hydrophobic, stable MOF composites. The MOFs are first coated with thin layers of polydopamine from free-base dopamine under a mild oxygen atmosphere, which then undergoes a Michael addition to covalently graft hydrophobic molecules to the external MOF surface. This easy, mild post-synthetic modification is shown to significantly improve the stability of a number of structurally diverse MOFs including HKUST-1 (Cu), ZIF-67 (Co), ZIF-8 (Zn), UiO-66 (Zr), Cu-TDPAT (Cu), Mg-MOF-74 (Mg) and MIL-100 (Fe) in wet, caustic (acidic and basic) environments as determined by powder X-ray diffraction and surface area measurements.

Chemically Cross-Linked MOF Membrane Generated from Imidazolium-Based Ionic Liquid-Decorated UiO-66 Type NMOF and Its Application toward CO2 Separation and Conversion.

Carbon dioxide capture and transformation are of great importance to make cuts in greenhouse gas emissions. Nanometal-organic frameworks (NMOFs) could serve as ideal fillers for polymer membranes owing to their structural diversity and regulable microenvironment of the nanocage. Herein, a bifunctional, robust, and chemically cross-linked NMOF-based membrane was successfully constructed by the postsynthetic polymerization of imidazolium-based ionic liquid (IL)-decorated UiO-66 type nanoparticles (NPs) and the isocyanate-terminated polyurethane oligomer under mild conditions. The IL-modified MOF-polymer membranes exhibit a highly selective adsorption for CO2 over N2 and CH4. In addition, the obtained membrane can also be a highly active heterogeneous catalyst for CO2 transformation by cycloaddition with epoxide under an ambient pressure.

The Postsynthetic Renaissance in Porous Solids.

Metal-organic frameworks (MOFs) have rapidly grown into a major area of chemical research over the last two decades. MOFs represent the development of covalent chemistry "beyond the molecule" and into extended structures. MOFs also present an unprecedented scaffold for performing heterogeneous organic transformations in the solid state, allowing for deliberate and precise preparation of new materials. The development of these transformations has given rise to the "postsynthetic renaissance", a suite of methods by which these materials can be transformed in a single-crystal-to-single-crystal manner. Postsynthetic modification, postsynthetic deprotection, postsynthetic exchange, postsynthetic insertion, and postsynthetic polymerization have exploited the unique features of both the organic and inorganic components of MOFs to create crystalline, porous solids of unique complexity and functionality.

Cross-linking Zr-based metal-organic polyhedra via postsynthetic polymerization.

Metal organic polyhedra (MOPs) have potential as supramolecular building blocks, but utilizing MOPs for postsynthetic polymerization has not been explored. Although MOPs with flexible organic moieties have been recently reported to target enhanced processability, permanent porosity has not been demonstrated. Here, a novel synthetic strategy involving the cross-linking of MOPs via a covalent bond is demonstrated by exploiting a condensation reaction between the MOP and flexible organic linkers. An amine-functionalized Zr-based MOP is cross-linked with acyl chloride linkers in the crystalline state to form cross-linked MOPs. The condensation reaction results in a cross-linked system without significant changes to the structure of the Zr-based MOP. Such cross-linked MOPs provide a microporous tetrahedral cage based on gas sorption analysis. This cross-linking strategy highlights the potential of MOPs as building blocks and provides access to a new class of porous material.

Post‐Synthetic Polymerization of UiO‐66‐NH2 Nanoparticles and Polyurethane Oligomer toward Stand‐Alone Membranes for Dye Removal and Separation

Metal-organic frameworks (MOFs) are widely used as porous materials in the fields of adsorption and separation. However, their practical application is largely hindered by limitations to their processability. Herein, new UiO-66-Urea-based flexible membranes with MOF loadings of 50 (1), 60 (2), and 70 wt % (3) were designed and prepared by post-synthetic polymerization of UiO-66-NH2 nanoparticles and a polyurethane oligomer under mild conditions. The adsorption behavior of membrane 3 towards four hydrophilic dyes, namely, eosin Y (EY), rhodamine B (RB), malachite green (MG), and methylene blue (MB), in aqueous solution was studied in detail. It exhibits strong adsorption of EY and RB but weak adsorption of MG and MB in aqueous solution. Owing to the selective adsorption of these hydrophilic dyes, membrane 3 can remove EY and RB from aqueous solution and completely separate EY/MB, RB/MG, and RB/MB mixtures in aqueous solution. In addition, the membrane is uniformly textured, easily handled, and can be reused for dye adsorption and separation.

Cover Picture: Photoinduced Postsynthetic Polymerization of a Metal-Organic Framework toward a Flexible Stand-Alone Membrane (Angew. Chem. Int. Ed. 14/2015)

Cover Picture: Photoinduced Postsynthetic Polymerization of a Metal-Organic Framework toward a Flexible Stand-Alone Membrane (Angew. Chem. Int. Ed. 14/2015)

Photoinduced Postsynthetic Polymerization of a Metal–Organic Framework toward a Flexible Stand‐Alone Membrane

AbstractMetal–organic frameworks (MOFs) are a promising class of nanoporous polymeric materials. However, the processing of such fragile crystalline powders into desired shapes for further applications is often difficult. A photoinduced postsynthetic polymerization (PSP) strategy was now employed to covalently link MOF crystals by flexible polymer chains, thus endowing the MOF powders with processability and flexibility. Nanosized UiO‐66‐NH2 was first functionalized with polymerizable functional groups, and its subsequent copolymerization with monomers was easily induced by UV light under solvent‐free and mild conditions. Because of the improved interaction between MOF particles and polymer chains, the resulting stand‐alone and elastic MOF‐based PSP‐derived membranes possess crack‐free and uniform structures and outstanding separation capabilities for CrVI ions from water.

Photoinduced postsynthetic polymerization of a metal-organic framework toward a flexible stand-alone membrane.

Metal-organic frameworks (MOFs) are a promising class of nanoporous polymeric materials. However, the processing of such fragile crystalline powders into desired shapes for further applications is often difficult. A photoinduced postsynthetic polymerization (PSP) strategy was now employed to covalently link MOF crystals by flexible polymer chains, thus endowing the MOF powders with processability and flexibility. Nanosized UiO-66-NH2 was first functionalized with polymerizable functional groups, and its subsequent copolymerization with monomers was easily induced by UV light under solvent-free and mild conditions. Because of the improved interaction between MOF particles and polymer chains, the resulting stand-alone and elastic MOF-based PSP-derived membranes possess crack-free and uniform structures and outstanding separation capabilities for Cr(VI) ions from water.