Metal‐Organic Framework Composites: From Fundamentals to Applications
TL;DR: The metal-organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands.
Abstract: Metal–organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.
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TL;DR: In this review, recent progress in MOF-based environmental sensors is introduced with a focus on optical, electrochemical, and field-effect transistor sensors.
Abstract: Increasing demand for timely and accurate environmental pollution monitoring and control requires new sensing techniques with outstanding performance, i.e., high sensitivity, high selectivity, and reliability. Metal-organic frameworks (MOFs), also known as porous coordination polymers, are a fascinating class of highly ordered crystalline coordination polymers formed by the coordination of metal ions/clusters and organic bridging linkers/ligands. Owing to their unique structures and properties, i.e., high surface area, tailorable pore size, high density of active sites, and high catalytic activity, various MOF-based sensing platforms have been reported for environmental contaminant detection including anions, heavy metal ions, organic compounds, and gases. In this review, recent progress in MOF-based environmental sensors is introduced with a focus on optical, electrochemical, and field-effect transistor sensors. The sensors have shown unique and promising performance in water and gas contaminant sensing. Moreover, by incorporation with other functional materials, MOF-based composites can greatly improve the sensor performance. The current limitations and future directions of MOF-based sensors are also discussed.
338 citations
TL;DR: It is concluded that 89Zr-UiO-66/Py-PGA-PEG-F3 can serve as an image-guidable, tumor-selective cargo delivery nanoplatform for in vivo positron emission tomography imaging and can find broad application in cancer theranostics.
Abstract: Nanoscale metal–organic frameworks (nMOF) materials represent an attractive tool for various biomedical applications. Due to the chemical versatility, enormous porosity, and tunable degradability of nMOFs, they have been adopted as carriers for delivery of imaging and/or therapeutic cargos. However, the relatively low stability of most nMOFs has limited practical in vivo applications. Here we report the production and characterization of an intrinsically radioactive UiO-66 nMOF (89Zr-UiO-66) with incorporation of positron-emitting isotope zirconium-89 (89Zr). 89Zr-UiO-66 was further functionalized with pyrene-derived polyethylene glycol (Py–PGA-PEG) and conjugated with a peptide ligand (F3) to nucleolin for targeting of triple-negative breast tumors. Doxorubicin (DOX) was loaded onto UiO-66 with a relatively high loading capacity (1 mg DOX/mg UiO-66) and served as both a therapeutic cargo and a fluorescence visualizer in this study. Functionalized 89Zr-UiO-66 demonstrated strong radiochemical and material...
205 citations
TL;DR: In this article, a facile route to rapidly assemble presynthesized UiO-66-NH2 crystals onto nonwoven polypropylene (PP) fibrous mats at ambient temperature was demonstrated.
Abstract: Highly tunable metal–organic framework (MOF) materials, including, for example, UiO-66-NH2, are known to be effective catalysts to degrade chemical warfare agents (CWAs) with half-lives near 1 min. Therefore, many researchers have been actively working on producing supported MOF materials to improve application effectiveness by using relatively slow solvothermal synthesis or repetitious stepwise layer-by-layer methods. Herein, we demonstrate a facile route to rapidly assemble presynthesized UiO-66-NH2 crystals onto nonwoven polypropylene (PP) fibrous mats at ambient temperature. Crystal assembly is chemically directed using β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTAB) as surfactant assembly agents, where the agents quickly (within 5 min) self-assemble on the crystal surface and promote physically robust chemical surface attachment while simultaneously impeding solution-phase crystal agglomeration. Furthermore, we find that when the PP is preconditioned using conformal metal oxide thin f...
159 citations
TL;DR: Of the materials explored, TiO2 ALD layers lead to the most effective overall MOF/fiber adhesion, uniformity, and a rapid catalytic degradation rate for a CWA simulant, dimethyl p-nitrophenyl phosphate (DMNP) with t1/2 = 15 min, 580-fold faster than the catalytic performance of untreated PP textiles.
Abstract: Metal–organic frameworks (MOFs) chemically bound to polymeric microfibrous textiles show promising performance for many future applications. In particular, Zr-based UiO-66-family MOF-textiles have been shown to catalytically degrade highly toxic chemical warfare agents (CWAs), where favorable MOF/polymer bonding and adhesion are attained by placing a nanoscale metal-oxide layer on the polymer fiber preceding MOF growth. To date, however, the nucleation mechanism of Zr-based MOFs on different metal oxides and how product performance is affected are not well understood. Herein, we provide new insight into how different inorganic nucleation films (i.e., Al2O3, ZnO, or TiO2) conformally coated on polypropylene (PP) nonwoven textiles via atomic layer deposition (ALD) influence the quality, overall surface area, and the fractional yield of UiO-66-NH2 MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO2 ALD layers lead to the most effective overall MOF/fiber adhesio...
142 citations
TL;DR: This review summarizes the progress made in the past years in the field of electrochemical and optical sensing based on the use of MOFs and the nanomaterial/MOF composites were discussed and related examples were presented.
Abstract: Metal–organic frameworks (MOFs) are porous coordination polymers (CP) produced by metal-based nodes and multitopic organic ligands. Based on their porous and microcrystalline powder structures, they have initially been used for storage, catalysis and separation. Then, because of their advantageous properties like ease of the tailoring, they also have been applied in areas like chemical sensing, biological applications, etc. The CPs were combined with molecules such as organic dyes, small biomolecules, nanomaterials like nanoparticles, nanowires, nanofibers and polymers and as a result, composite MOFs have been produced. By this way, better mechanical stability, conductivity, and catalytic performance were obtained. This review (with 135 refs.) summarizes the progress made in the past years in the field of electrochemical and optical sensing based on the use of MOFs. Following an introduction into the field, large sections cover MOF based sensors exploiting (a) carbon nanomaterials (with subsections on carbon nanotubes, graphene and its derivatives), (b) metal/metal oxide MOFs; including gold, silver, copper and/or copper oxide nanoparticle and other metal/MOF composites. Enzyme mimicking MOFs are discussed next. In this context, after the brief information about focused MOFs, the nanomaterial/MOF composites were discussed and related examples were presented.
121 citations
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TL;DR: The synthesis, chemical modification and potential applications of MOFs have been reviewed previously, and there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed.
Abstract: Metal–organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.
376 citations