Nanorods of PCN-222, a large-pore, zirconium-based porphyrinic metal-organic framework (MOF), have been prepared through coordination modulation-controlled crystal growth through competing monodentate ligands known as modulators-for incorporation into reverse osmosis thin-film nanocomposite (TFN) membranes. Postsynthetic modification of the MOF node through binding of myristic acid (MA) altered channel dimensions and pore size distribution. The extent of MOF modification was characterized through Brunauer-Emmett-Teller gas sorption and 1H NMR following digestion of the particles. TFN membranes containing PCN-222 nanoparticles modified with varying levels of MA were fabricated via dispersion in the aqueous phase during interfacial polymerization, and the resulting flux and rejection performance of each membrane were evaluated. Increased water flux was observed with increasing MA content in the PCN-222 nanorods. Up to 95% increase in water flux was observed for a TFN containing 0.01 wt % loading of PCN-222 nanorods with a 10:1 MA to linker ratio, while maintaining high salt rejection. The flux change was attributed to tunable water transport through the nanorod pore structure and also through rapid water transport pathways at the nanorod-polymer interface.
Keywords: desalination; metal−organic framework; nanoparticles; reverse osmosis; thin-film composite; thin-film nanocomposite.