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Relevant academic research and scientific papers

Thiol-ene photopolymerization of vinyl-functionalized metal-organic frameworks towards mixed-matrix membranes

We developed a facile methodology for fabricating a free-standing mixed-matrix membrane (MMM) containing covalently incorporated metal-organic framework (MOF) particles up to 60 wt% by utilizing thiol-ene photopolymerization with the MOF consisting of vinyl functionality. Vinyl-functionalized UiO-66 (UiO-66-CH═CH2) was synthesized from 2-vinyl-1,4-dicarboxylic acid with ZrCl4, and a free-standing MMM was readily produced by irradiation of a polymerization mixture containing UiO-66-CH═CH2, poly(ethylene glycol) divinyl ether (PEO-250), pentaerythritol tetra(3-mercaptopropionate) (PETM), 2,2′-(ethylenedioxy)diethanethiol (EDDT), and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoradical initiator. Assorted analyses combining FTIR, thermogravimetric analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction strongly supported the fact that the desired MMM containing well-dispersed UiO-66-CH═CH2 particles was successfully produced by C-S bond formation, which provided strong union of the MOF with the polymer matrix without interfacial voids. The produced MMM was highly flexible and showed improved mechanical properties as compared to the pristine polymeric membrane, indicating that the covalently immobilized UiO-66-CH═CH2 particles were homogeneously distributed in the polymer matrix. Gas permeability across the MMM was significantly enhanced compared with the pristine polymeric membrane as diffusion of the gas molecules was facilitated in the porous space in the MOF.

Synthesis of: O-carborane-functionalized metal-organic frameworks through ligand exchanges for aggregation-induced emission in the solid state

The carborane (CB)-functionalized ligand was installed in a variety of MOFs through postsynthetic ligand exchange processes. This methodology is a general method for preparing o-CB-functionalized MOFs with known frameworks. Furthermore, the photoluminescence (PL) spectra revealed intriguing aggregation-induced emission (AIE) features following the systematic incorporation of o-CB functionalities into framework-type materials.

Nickel?alkyne?functionalized metal?organic frameworks: An efficient and reusable catalyst

Electron-donating groups in the robust MOF motif are able to provide an excellent catalytic platform, therefore obtaining site-isolated metal sites. In this study, the terminal alkyne is firstly introduced into UiO-66-type metal-organic frameworks (UiO-66-alkyne). Herein, to further study the application potential of this material, a covalently bonded nickel catalyst based on the alkynyl-tagged UiO-66-alkyne has been prepared and afforded us unprecedented highly dispersed and highly efficient catalytic active species. Meanwhile, this nickel-contained catalyst method for joining metals provided an alternative pathway regarding catalyst designing. With UiO-66-alkyne-Ni, the heterogeneous transformation of homogeneous catalysts is realized. Using benzaldehyde and malononitrile as starting materials, we were able to catalyze the Knoevenagel condensation within 45 min under room temperature with yield (> 99 %). Moreover, the recovery rate of the UiO-66-alkyne-Ni also outperformed previous MOFs in both small-scale and gram-level reactions, which shows UiO-66-alkyne-Ni is a potential contributor to the subsequent industrialization.

A covalent modification strategy for di-alkyne tagged metal-organic frameworks to access efficient heterogeneous catalysts toward C-C bond formation

Organic and inorganic building blocks are used to construct a class of metal-organic frameworks (MOFs) that exhibit tremendous chemical tunability. In this study, a novel zirconium-based MOF UiO-66-(alkyne)2 with a di-alkyne tag was obtained through solvothermal pre-synthesis, which provides a potential covalent binding site for post-synthesis modification. On this basis, a gentle post-synthesis modification strategy based on covalency was expanded for introducing diverse metals, and a family of isostructural tailored materials (UiO-66-alkyne-Co, UiO-66-(alkyne-Co)2 and UiO-66-(alkyne-Ni)2) with base metals Ni or Co were designed and synthesized successfully. Among them, di-alkyne tagged UiO-66-(alkyne-Co)2 has shown unprecedented remarkable performance as a heterogeneous catalyst for the Knoevenagel reaction, completely converting benzaldehyde in just 5 min at room temperature, to our knowledge, faster than the reported MOF catalysts. Moreover, UiO-66-(alkyne-Co)2 maintains high stability and functionality after five cycles, and the catalytic activity is also preserved in the gram level scale-up experiment, indicating that UiO-66-(alkyne-Co)2 has great potential for practical application in the formation of C-C bonds. In a sense, this research provides an ideal platform for anchoring the required functional groups on alkyne-modified MOFs, which lays a foundation for finding more potential applications of MOF materials in the future.