Issue 20, 2018

An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

Abstract

We present a comprehensive investigation of the CO2 adsorption properties of an isostructural series of metal–organic frameworks, M-BTT (M = Cr, Mn, Fe, Cu; BTT3− = 1,3,5-benzenetristetrazolate), which exhibit a high density of open metal sites capable of polarizing and binding guest molecules. Coupling gas adsorption measurements with in situ neutron and X-ray diffraction experiments provides molecular-level insight into the adsorption process and enables rationalization of the observed adsorption isotherms. In particular, structural data confirms that the high initial isosteric heats of CO2 adsorption for the series are directly correlated with the presence of open metal sites and further reveals the positions and orientations of as many as three additional adsorption sites. Density functional theory calculations that include van der Waals dispersion corrections quantitatively support the observed structural features associated with the primary and secondary CO2 binding sites, including CO2 positions and orientations, as well as the experimentally determined isosteric heats of CO2 adsorption.

Graphical abstract: An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

Supplementary files

Article information

Article type
Edge Article
Submitted
28 Feb 2018
Accepted
22 Apr 2018
First published
23 Apr 2018
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., 2018,9, 4579-4588

An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

M. Asgari, S. Jawahery, E. D. Bloch, M. R. Hudson, R. Flacau, B. Vlaisavljevich, J. R. Long, C. M. Brown and W. L. Queen, Chem. Sci., 2018, 9, 4579 DOI: 10.1039/C8SC00971F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements