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

DOI: 10.1039/C5DT03477A
PMID: 26575842

Authors: Emma F Baxter (University of Cambridge) , Thomas D. Bennett (University of Cambridge) , Andrew B. Cairns (University of Oxford) , Nick J. Brownbill (University of Liverpool) , Andrew L. Goodwin (University of Oxford) , David A. Keen (ISIS Facility) , Philip A Chater (Diamond Light Source) , Frédéric Blanc (University of Liverpool) , Anthony K. Cheetham (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Dalton Transactions

State: Published (Approved)
Published: November 2015
Diamond Proposal Number(s): 9691

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 113Cd NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor

Subject Areas: Chemistry


Instruments: I15-Extreme Conditions