Selective Gas Uptake and Rotational Dynamics in a (3,24)-Connected Metal–Organic Framework Material | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

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

Trenholme William J.F. ^1,2 , Kolokolov Daniil I. ^3,4 , Bound Michelle ² , Argent Stephen P. ² , Gould Jamie A. ^2,5 , Li Jiangnan ¹ , Barnett Sarah A. ⁶ , Blake Alexander J. ² , Stepanov Alexander G. ^3,4 , Besley Elena ² , Easun Timothy L. ^2,7 , Yang Sihai ¹ , Schröder Martin ¹

Affiliations

1	School of Chemistry, University of Manchester, Manchester M13 9PL, U.K.
2	School of Chemistry, University of Nottingham, Nottingham NG7 2RD, U.K.
3	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090, Russia
4	Novosibirsk State University, Novosibirsk 630090, Russia
5	Faculty of Science, Agriculture and Engineering, Newcastle University, Newcastle upon Tyne NE1 7RU, U.K.
6	Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, U.K.
7	School of Chemistry, Cardiff University, Cardiff CF10 3AT, U.K

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

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.

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

Submitted:	Oct 24, 2020
Published online:	Feb 24, 2021
Published print:	Mar 10, 2021

Web of science:	WOS:000629075900013
Scopus:	2-s2.0-85102965139
Elibrary:	46758113
Chemical Abstracts:	2021:487605
PMID:	33625838
OpenAlex:	W3127595512

DB	Citing
Web of science	37
Scopus	39
Elibrary	38
OpenAlex	44