Phys Chem Chem Phys. 2016 Jan 21;18(3):2192-201. doi: 10.1039/c5cp06798g.

Connecting defects and amorphization in UiO-66 and MIL-140 metal–organic frameworks: a combined experimental and computational study.

Physical chemistry chemical physics : PCCP

Thomas D Bennett, Tanya K Todorova, Emma F Baxter, David G Reid, Christel Gervais, Bart Bueken, B Van de Voorde, Dirk De Vos, David A Keen, Caroline Mellot-Draznieks

PMID: 27144237 DOI: 10.1039/c5cp06798g

Abstract

The mechanism and products of the structural collapse of the metal–organic frameworks (MOFs) UiO-66, MIL-140B and MIL-140C upon ball-milling are investigated through solid state 13C NMR and pair distribution function (PDF) studies, finding amorphization to proceed by the breaking of a fraction of metal–ligand bonding in each case. The amorphous products contain inorganic–organic bonding motifs reminiscent of the crystalline phases. Whilst the inorganic Zr6O4(OH)4 clusters of UiO-66 remain intact upon structural collapse, the ZrO backbone of the MIL-140 frameworks undergoes substantial distortion. Density functional theory calculations have been performed to investigate defective models of MIL-140B and show, through comparison of calculated and experimental 13C NMR spectra, that amorphization and defects in the materials are linked.

Publication Types

• Journal Article
• Research Support, Non-U.S. Gov't