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Rapid, clean and scalable synthesis of microporous functional MOFs and their non- conventional forms via mechanochemistry

Porous metal-organic frameworks (MOFs)[1] are one of the most researched areas of modern materials science. These modular materials, whose structure and properties can be readily altered by careful choice of metal nodes and suitable organic linkers, are widely studied for gas storage and separation, catalysis, sensing, light-harvesting, and other applications.[2] The growing number of studies in the field resulted in the recent commercialization of several microporous MOFs on a laboratory scale. However, the standard synthetic procedures, involving an excess of organic solvents and harsh reaction conditions, still prevent their wider industrial application. Here we present the application of mechanochemical reactions, [3] i.e., reactions between solid reactants induced by mechanical force, for a rapid, green and room-temperature transformation of environmentally safe metal precursors, oxides or hydroxides into most relevant microporous MOFs, such as HKUST-1, [4] MOF-74[5] or zirconium-based MOFs of UiO, [6] and NU-[7] families. Mechanochemistry allows even for rapid and efficient synthesis and polymorphic control in complex porphyrinic zirconium MOFs.[8] We show here how the milling produces high-quality zirconium MOFs quantitatively in multigram quantities by using only a catalytic amount of "green" liquids, such as methanol or water.[9]

Mechanochemistry ; non-conventional MOFs ; mixed-metal MOFs ; green synthesis

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