Synthesis, characterization, and tunable adsorption and diffusion properties of hybrid ZIF ‐7‐90 frameworks

Hybrid zeolitic imidazolate frameworks (ZIFs), containing more than one type of imidazolate linker, can allow highly tunable molecular sieving and adsorption. Their crystallization becomes more challenging when the end‐member (single‐linker) ZIFs crystallize in different crystal systems. We demonstrate the controlled synthesis and detailed characterization of hybrid ZIF‐7‐90 frameworks containing linkers of ZIF‐7 (rhombohedral) and ZIF‐90 (cubic). ZIF‐7‐90 materials with SOD‐type topology are obtained in three crystalline phases depending on the linker composition and synthesis technique. The effect of synthesis conditions on the activation‐induced phase transition from rhombohedral to other topologies is studied. Nitrogen physisorption at 77 K and CO2 physisorption at 273 K shows the tunability of the pore‐size distribution and the framework flexibility as a function of framework composition. Measurements of water adsorption and butane isomer diffusion illustrate the tunability of diffusivity over seven orders of magnitude and control of hydrophobic to hydrophilic adsorption behavior.