Issue 12, 2017

Bond breakage under pressure in a metal organic framework


The internal free volume of porous materials diminishes upon mechanical compression, and such volume collapse can have chemical consequences. We report here the endothermic bond breakage in a metal-organic framework (MOF) during compression-induced collapse. Upon bulk compression at 1.9 GPa, the effective number for Zr–O bonds between Zr(IV) ions and carboxylate groups in UiO-66 decreased from 4.0 to 1.9, as determined by EXAFS, and the internal free volume was synchronously collapsed. Consistent with the EXAFS data, IR spectra confirmed conversion of synsyn bridging carboxylates to monodentate ligation, thus establishing mechanochemical reactions induced by external compression of MOFs. Substantial mechanical energy (∼4 kJ g−1) was absorbed by UiO-66 nanocrystals during compression, as demonstrated from nanocompression of single crystals (600 nm) in situ during scanning electron microscopy, which establishes the potential application of MOFs as mechanical energy absorbers for hydrostatic and shock compression.

Graphical abstract: Bond breakage under pressure in a metal organic framework

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Article information

Article type
Edge Article
29 Aug 2017
28 Sep 2017
First published
09 Oct 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 8004-8011

Bond breakage under pressure in a metal organic framework

Z. Su, Y. Miao, G. Zhang, J. T. Miller and K. S. Suslick, Chem. Sci., 2017, 8, 8004 DOI: 10.1039/C7SC03786D

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