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Binding and separation of CO2, SO2 and C2H2 in homo- and hetero-metallic metal-organic framework materials

Briggs, Lydia, Newby, Ruth, Han, Xue, Morris, Christopher G., Savage, Mathew, Krap, Cristina Perez, Easun, Timothy L., Frogley, Mark D., Cinque, Gianfelice, Murray, Claire A., Tang, Chiu C., Sun, Junliang, Yang, Sihai and Schröder, Martin 2021. Binding and separation of CO2, SO2 and C2H2 in homo- and hetero-metallic metal-organic framework materials. Journal of Materials Chemistry A 9 (11) , pp. 7190-7197. 10.1039/D1TA00687H

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We report the adsorption of C2H2, CO2 and SO2 in a new, ultra-stable Cr(III)-based MOF, MFM-300(Cr), {[Cr2(OH)2(L)], H4L = biphenyl-3,3′,5,5′-tetracarboxylic acid}. MFM-300(Cr) shows uptakes of 7.37, 7.73 and 8.59 mmol g−1 for CO2, C2H2 and SO2, respectively, at 273 K, 1.0 bar, and shows a higher selectivity for SO2/CO2 compared with the Al(III) analogue MFM-300(Al) (selectivity of 79 vs. 45). In order to monitor the effects of changing metal centre on gas uptake and to integrate the properties of the homometallic analogues, the mixed metal MFM-300(Al0.67Cr0.33), [Al1.34Cr0.66(OH)2(L)] has been synthesised. In situ synchrotron micro-FTIR spectroscopy has identified distinct CO2 binding environments on Al–O(H)–Al, Cr–O(H)–Cr and Al–O(H)–Cr bridges in MFM-300(Al0.67Cr0.33), and we have determined the binding domains for these gases by in situ synchrotron X-ray diffraction in both MFM-300(Cr) and MFM-300(Al0.67Cr0.33). The capability of these materials for gas separation has been confirmed by dynamic breakthrough experiments. The incorporation of Al(III) and Cr(III) within the same framework allows tuning of the host–guest and guest–guest interactions within these functional porous materials.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Royal Society of Chemistry
ISSN: 2050-7488
Funders: EPSRC, EU Horizon 2020 and Royal Society
Date of First Compliant Deposit: 6 April 2021
Date of Acceptance: 15 February 2021
Last Modified: 07 Apr 2021 15:31

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