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Issue 3, 2015
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Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

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Abstract

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)2(PPh3)2 as well as the commercially important metal organic frameworks (MOFs) Cu3(BTC)2 (HKUST-1), Zn(2-methylimidazolate)2 (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h−1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h−1. The space time yields (STYs) for these methods of up to 144 × 103 kg per m3 per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

Graphical abstract: Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

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Publication details

The article was received on 20 Oct 2014, accepted on 07 Jan 2015 and first published on 08 Jan 2015


Article type: Edge Article
DOI: 10.1039/C4SC03217A
Chem. Sci., 2015,6, 1645-1649
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

    D. Crawford, J. Casaban, R. Haydon, N. Giri, T. McNally and S. L. James, Chem. Sci., 2015, 6, 1645
    DOI: 10.1039/C4SC03217A

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