Benign by Design: Green and Scalable Synthesis of Zirconium UiO-Metal–Organic Frameworks by Water-Assisted Mechanochemistry

By Bahar Karadeniz, Ashlee J. Howarth, T. Stolar, Timur Islamoglu, I. Dejanović, Martina Tireli, Megan C. Wasson, Su-Young Moon, O. Farha, T. Friščić and 1 more. ACS Sustainable Chemistry and Engineering, 2018

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We present a solvent-free, green, and rapid mechanochemical route for the synthesis of a series of zirconium metal–organic frameworks (MOFs) composed of Zr6 cluster nodes, UiO-66, UiO-66-NH2, MOF-801, and MOF-804, both on a laboratory scale and by scalable and flow mechanochemical processing. The methodology, based on the use of a nonconventional zirconium dodecanuclear acetate cluster and a minute amount of water as an additive, affords high-quality MOFs in less than 1 h of milling, with minimal requirements for workup processing and eliminating the need for conventional hazardous solvents, such as dimethylformamide. Moreover, the use of a dodecanuclear zirconium acetate precursor circumvents the need for modulators resulting in acetic acid as the only byproduct of the reaction, which does not harm these acid-resistant materials. The porosity, thermal and chemical stability, as well as catalytic activity of mechanochemically prepared Zr-based MOFs are similar to those of solvothermally synthesized counte...

Subfields: Inorganic Chemistry, Materials Chemistry, Physical and Theoretical Chemistry

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