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

Karadeniz, Bahar; Howarth, Ashlee J.; Stolar, Tomislav; Islamoglu, Timur; Dejanović, Igor; Tireli, Martina; Wasson, Megan C.; Moon, Su-Young; Farha, Omar K.; Friščić, Tomislav; Užarević, Krunoslav (2018) Benign by Design: Green and Scalable Synthesis of Zirconium UiO-Metal–Organic Frameworks by Water-Assisted Mechanochemistry. ACS Sustainable Chemistry and Engineering, 6 (11). pp. 15841-15849. ISSN 2168-0485

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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 counterparts. Finally, the synthesis is readily applicable on a 10 g scale by using a planetary mill, and is also performed by solid-state flow synthesis using twin-screw extrusion (TSE), affording more than 100 g of catalytically active UiO-66-NH2 material in a continuous process at a rate of 1.4 kg/h.

Item Type: Article
Additional Information: This work has been supported by the Croatian Science foundation (Grant 4744). We would like to thank the Adris foundation for the FTIR-ATR spectrometer. T.F. acknowledges the financial support of the NSERC Discovery Grant (RGPIN-2017-06467) and the NSERC E. W. R. Steacie Memorial Fellowship (SMFSU 507347-17). O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003).
Uncontrolled Keywords: mechanochemistry; ball-milling; twin-screw extrusion; reactive extrusion; MOF; zirconium MOF; UiO-66; catalysis
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Mehaniokemijska reaktivnost pod kontroliranim uvjetima temperature i atmosfere za čišću sintezu funkcionalnih materijala-MECHANOCONTROLKrunoslav UžarevićUIP-2014-09-4744HRZZ
Depositing User: Krunoslav Užarević
Date Deposited: 28 Nov 2019 13:50
DOI: 10.1021/acssuschemeng.8b04458

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