Issue 20, 2020

Observation of binding of carbon dioxide to nitro-decorated metal–organic frameworks

Abstract

Metal–organic frameworks (MOFs) functionalised with amine, amide and hydroxyl groups show great promise for CO2 binding due to their ability to form hydrogen bonds to CO2. Herein we report the adsorption and selectivity of CO2 in four iso-reticular MOFs adopting the NbO topology. Functionalisation of the parent MOF, MFM-102, with –NO2, –NH2 and alkyl groups leads to an enhancement of CO2 adsorption of up to 36% for the NO2-decorated MOF and with raised selectivity. MFM-102-NO2 shows the highest adsorption capacity for CO2 (184 cm3 g−1 at 273 K and 1.0 bar) within this series, comparable to the best-behaving iso-reticular MOFs. At 298 K and 1.0 bar, MFM-102-NO2 shows a CO2/CH4 selectivity of 5.0. In situ inelastic neutron scattering and synchrotron FT-IR micro-spectroscopy were employed to elucidate the host–guest interaction dynamics within CO2-loaded MFM-102-NO2. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-102-NO2, and, to the best of our knowledge, we report the first example of CO2 binding to a –NO2 group in a porous MOF. Synergistic effects between the –NO2 group and the open metal sites lead to optimal binding of CO2 molecules within MFM-102-NO2via hydrogen bonding to C–H groups.

Graphical abstract: Observation of binding of carbon dioxide to nitro-decorated metal–organic frameworks

Supplementary files

Article information

Article type
Edge Article
Submitted
25 8月 2019
Accepted
26 2月 2020
First published
14 5月 2020
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., 2020,11, 5339-5346

Observation of binding of carbon dioxide to nitro-decorated metal–organic frameworks

T. D. Duong, S. A. Sapchenko, I. da Silva, H. G. W. Godfrey, Y. Cheng, L. L. Daemen, P. Manuel, M. D. Frogley, G. Cinque, A. J. Ramirez-Cuesta, S. Yang and M. Schröder, Chem. Sci., 2020, 11, 5339 DOI: 10.1039/C9SC04294F

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