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Issue 20, 2020
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Observation of binding of carbon dioxide to nitro-decorated metal–organic frameworks

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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

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Supplementary files

Article information


Submitted
25 Aug 2019
Accepted
26 Feb 2020
First published
14 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 5339-5346
Article type
Edge Article

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

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.

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