MOFs are commonly hydrophilic because of their formation which positive charged metal ion combined with negative charged organic linkers. UIO-66, a popular MOF example, is zirconium based MOF consisting of zirconium metal ion with terephthalic acid as a linker. Due to the Zr-O and OH bonds, UIO-66 has high affinity with polar solvent groups. Most recently, much have been attempted to obtain hydrophobically stabilized MOFs in order to mix with non-polar polymers. The common approaches are functionalizing of MOF surface using by hydrophobic ligands or mixing with hydrophobic compounds such as carbon, polydimethylsiloxane, and silica. However, these types of MOFs necessarily demonstrated decreased adsorption capacity, catalytic activity and unexpected influence to their structure and pore channel on the surfaces. To solve these problems, we sought to find a substance that protects the porosity and accessibility of MOFs. Here we report a surface modification route for MOFs to disperse in the non-polar solvent and separate the small particles from the mixture. We focused on the UIO-66 MOF particle with 4-tertbutylcalix[n]arenes. As synthesized UIO-66 with different amount of calix[n]arene conditions (0 to 30 wt%) were investigated in toluene. Adsorption isotherms, particles dispersity, particle size distributions, and kinetics have been studied in detail. We show that supramolecular amphiphilic structures can effectively form stable colloidal dispersions of MOFs provided that their sites are larger than the pore openings. Our findings could lead to universal methodology to form non-polar stable dispersion of MOFs, to be used particularly in mixed matrix membranes.<br/>

Surface and porosity modification of UIO-66 nanostructures using calixarenes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.