Isoreticular metal-organic frameworks and their membranes with enhanced crack resistance and moisture stability by surfactant-assisted drying.

Here we report a new strategy that can not only prevent the formation of cracks and fractures in the crystals and films of metal-organic frameworks (MOFs) but also substantially enhance their stability with respect to moisture. It involves the addition of surfactants during a drying process. Surfactants reduce interfacial tension, thereby repressing the formation of fractures and cracks during the final drying process. It was found that, once dried, surfactants adsorbed on the crystal surface render the surface hydrophobic, leading to the enhancement in the stability toward moisture. Using this new strategy, the first crack-free IRMOF-3 membrane was successfully prepared, and its gas permeation performance was tested. IRMOF-3 membranes are found to favor CO2 over C3H8 mainly due to the affinity of CO2 to the amine groups in the structure. In addition, crack-free IRMOF-3 membranes were postsynthetically modified with heptanoic anhydride, thereby changing the effective pore size and surface property of the MOF. Once modified with the anhydride, the membranes favor C3H8 over CO2 due to the increased solubility of C3H8 in the presence of the hydrocarbon moiety.