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

Published

May 28, 2018

Author(s)

Mehrdad Asgari, Sudi Jawahery, Eric D. Bloch, Matthew R. Hudson, Roxana Flacau, Bess Vlaisavljevich, Jeffrey R. Long, Craig Brown, Wendy L. Queen

Abstract

We present a comprehensive investigation of the CO₂ adsorption properties of the isostructural series of metal-organic frameworks M-BTT (M =Cr, Mn, Fe, Cu, BTT^3- = 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 isoteric 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 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.

Citation

Chemical Science

Volume

9

Issue

20

Pub Type

Journals

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Keywords

neutron diffraction, crystallography, adsorption isotherms, carbon dioxide

Citation

Asgari, M. , Jawahery, S. , Bloch, E. , Hudson, M. , Flacau, R. , Vlaisavljevich, B. , Long, J. , Brown, C. and Queen, W. (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, Chemical Science, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=925613 (Accessed October 26, 2025)