In the last decade zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs), have been rising in popularity due to their diverse topologies, good thermal and chemical stability, and large pore volumes, which could enable their use for gas-storage, separation of gases, and catalysis.1 However, traditional solution synthesis methods are very energy demanding, they use large quantities of organic solvents and rather expensive inorganic nitrates as starting material, and, above all, are often irreproducible and hard to control, giving mixtures of different ZIF frameworks in often low yields. Mechanochemical alternatives have been proposed, including neat grinding2, ion and liquid assisted grinding (ILAG)3, and most recently, accelerated aging4. We explored several different methods for solid-state ZIF synthesis, including neat and liquid-assisted grinding, slurrying, as well as a modified accelerated aging procedure. We show that starting from nanoparticulate zinc oxide, and utilizing mechanochemical activation in conjunction with a macrocyclic template, we can reproducibly direct the outcome of ZIF syntheses to frameworks containing a specific structural motif. [1] Park, K.S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H.H.; O’Keeffe, M.; Yaghi, O. M. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 10186–10191. [2] Tanaka, S.; Kida, K.; Nagaoka, T.; Otaa, T.; Miyake, Y.; Chem. Commun., 2013, 49, 7884-7886. [3] Beldon, P. J.; Fabian, L.; Stein, R. S.; Thirumurugan, A.; Cheetham, A. K.; Friščić, T. Angew. Chem. Int. Ed. 2010, 46, 9640–9643 [4] Cliffe, M. J.; Mottillo, C.; Stein, R. S.; Bučar, D.-K.; Friščić, T. Chem. Sci., 2012, 3, 2495.

Solid-state reactivity of nanoparticulate ZnO in templated ZIF synthesis

251st National Meeting (2016)

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