Selective Gas Uptake and Rotational Dynamics in a (3,24)-Connected Metal–Organic Framework Material Full article
Journal |
Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126 |
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Output data | Year: 2021, Volume: 143, Number: 9, Pages: 3348-3358 Pages count : 11 DOI: 10.1021/jacs.0c11202 | ||||||||||||||
Tags | CARBON-DIOXIDE; POLYHEDRAL FRAMEWORKS; C-2 HYDROCARBONS; HIGH-CAPACITY; SURFACE-AREA; SEPARATION; CO2; STORAGE; MOF; ADSORPTION | ||||||||||||||
Authors |
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Affiliations |
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Funding (9)
1 | Royal Society | IE150114 |
2 | Russian Science Foundation | 17-73-10135 |
3 | Ministry of Science and Higher Education of the Russian Federation | 0239-2021-0003 |
4 | Engineering and Physical Sciences Research Council | |
5 | University of Nottingham | |
6 | University of Manchester | |
7 | European Commission | 742401 NANOCHEM |
8 | Royal Society | |
9 | China Scholarship Council |
Abstract:
The desolvated (3,24)-connected metal–organic framework (MOF) material, MFM-160a, [Cu3(L)(H2O)3] [H6L = 1,3,5-triazine-2,4,6-tris(aminophenyl-4-isophthalic acid)], exhibits excellent high-pressure uptake of CO2 (110 wt% at 20 bar, 298 K) and highly selective separation of C2 hydrocarbons from CH4 at 1 bar pressure. Henry’s law selectivities of 79:1 for C2H2:CH4 and 70:1 for C2H4:CH4 at 298 K are observed, consistent with ideal adsorption solution theory (IAST) predictions. Significantly, MFM-160a shows a selectivity of 16:1 for C2H2:CO2. Solid-state 2H NMR spectroscopic studies on partially deuterated MFM-160-d12 confirm an ultra-low barrier (∼2 kJ mol–1) to rotation of the phenyl group in the activated MOF and a rotation rate 5 orders of magnitude slower than usually observed for solid-state materials (1.4 × 106 Hz cf. 1011–1013 Hz). Upon introduction of CO2 or C2H2 into desolvated MFM-160a, this rate of rotation was found to increase with increasing gas pressure, a phenomenon attributed to the weakening of an intramolecular hydrogen bond in the triazine-containing linker upon gas binding. DFT calculations of binding energies and interactions of CO2 and C2H2 around the triazine core are entirely consistent with the 2H NMR spectroscopic observations.
Cite:
Trenholme W.J.F.
, Kolokolov D.I.
, Bound M.
, Argent S.P.
, Gould J.A.
, Li J.
, Barnett S.A.
, Blake A.J.
, Stepanov A.G.
, Besley E.
, Easun T.L.
, Yang S.
, Schröder M.
Selective Gas Uptake and Rotational Dynamics in a (3,24)-Connected Metal–Organic Framework Material
Journal of the American Chemical Society. 2021. V.143. N9. P.3348-3358. DOI: 10.1021/jacs.0c11202 WOS Scopus РИНЦ AN PMID OpenAlex
Selective Gas Uptake and Rotational Dynamics in a (3,24)-Connected Metal–Organic Framework Material
Journal of the American Chemical Society. 2021. V.143. N9. P.3348-3358. DOI: 10.1021/jacs.0c11202 WOS Scopus РИНЦ AN PMID OpenAlex
Dates:
Submitted: | Oct 24, 2020 |
Published online: | Feb 24, 2021 |
Published print: | Mar 10, 2021 |
Identifiers:
Web of science: | WOS:000629075900013 |
Scopus: | 2-s2.0-85102965139 |
Elibrary: | 46758113 |
Chemical Abstracts: | 2021:487605 |
PMID: | 33625838 |
OpenAlex: | W3127595512 |