NDLI: A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Blanc, Frédéric Keen, David A. Cheetham, Anthony K. Baxter, Emma F. Brownbill, Nick J. Chater, Philip A. Goodwin, Andrew L. Cairns, Andrew B. Bennett, Thomas D.
Description	Author Affiliation: Baxter EF ( Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3 0FS, UK. akc30@cam.ac.uk.); Bennett TD ( Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3 0FS, UK. akc30@cam.ac.uk.); Cairns AB ( Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.); Brownbill NJ ( Department of Chemistry and Stephenson Institute for Renewable Energy, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.); Goodwin AL ( Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.); Keen DA ( ISIS Facility, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, OX11 0QX, UK.); Chater PA ( Diamond Light Source Ltd, Diamond House, Harwell Science & Innovation Campus, Didcot, Oxfordshire, OX11 0DE, UK.); Blanc F ( Department of Chemistry and Stephenson Institute for Renewable Energy, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.); Cheetham AK ( Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3 0FS, UK. akc30@cam.ac.uk.)
Abstract	X-ray diffraction has been used to investigate the kinetics of amorphization through ball-milling at 20 Hz, for five zeolitic imidazolate frameworks (ZIFs) – ZIF-8, ZIF-4, ZIF-zni, BIF-1-Li and CdIF-1. We find that the rates of amorphization for the zinc-containing ZIFs increase with increasing solvent accessible volume (SAV) in the sequence ZIF-8 > ZIF-4 > ZIF-zni. The Li–B analogue of the dense ZIF-zni amorphizes more slowly than the corresponding zinc phase, with the behaviour showing a correlation with their relative bulk moduli and SAVs. The cadmium analogue of ZIF-8 (CdIF-1) amorphizes more rapidly than the zinc counterpart, which we ascribe primarily to its relatively weak M–N bonds as well as the higher SAV. The results for the ZIFs are compared to three classical zeolites – Na-X, Na-Y and ZSM-5 – with these taking up to four times longer to amorphize. The presence of adsorbed solvent in the pores is found to render both ZIF and zeolite frameworks more resistant to amorphization. X-ray total scattering measurements show that amorphous ZIF-zni is structurally indistinguishable from amorphous ZIF-4 with both structures retaining the same short-range order that is present in their crystalline precursors. By contrast, both X-ray total scattering measurements and $^{113}Cd$ NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor.
ISSN	14779226
Issue Number	10
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-03-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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