Porous Metal–Organic Polyhedral Frameworks with Optimal Molecular Dynamics and Pore Geometry for Methane Storage | Sciact - CRIS-system of Boreskov Institute of Catalysis

Porous Metal–Organic Polyhedral Frameworks with Optimal Molecular Dynamics and Pore Geometry for Methane Storage Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2017, Volume: 139, Number: 38, Pages: 13349-13360 Pages count : 12 DOI: 10.1021/jacs.7b05453

Tags

ISOPHTHALATE LINKERS; HYDROGEN STORAGE; WORKING CAPACITY; NATURAL-GAS; ROTORS; SEPARATIONS; DIFFRACTION; CHEMISTRY; MECHANISM; POROSITY

Authors

Yan Yong ¹ , Kolokolov Daniil I. ^2,3 , da Silva Ivan ⁴ , Stepanov Alexander G. ^2,3 , Blake Alexander J. ⁵ , Dailly Anne ⁶ , Manuel Pascal ⁴ , Tang Chiu C. ⁷ , Yang Sihai ¹ , Schröder Martin ^1,8

Affiliations

1	School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom
2	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
3	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
4	ISIS Facility, Science and Technology Facilities Council (STFC), Rutherford Appleton Laboratory, Didcot, OX11 0QX, United Kingdom
5	School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom
6	Chemical and Environmental Sciences Laboratory, General Motors Corporation, Warren, Michigan 48090, United States
7	Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, United Kingdom
8	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Avenue, Novosibirsk 630090, Russia

Funding (6)

1	Federal Agency for Scientific Organizations	0303-2016-0003
2	Engineering and Physical Sciences Research Council
3	The Ministry of Education and Science of the Russian Federation	14.Z50.31.0006
4	European Research Council	226593
5	Engineering and Physical Sciences Research Council	EP/I011870
6	Royal Society	IE150114

Natural gas (methane, CH4) is widely considered as a promising energy carrier for mobile applications. Maximizing the storage capacity is the primary goal for the design of future storage media. Here we report the CH4 storage properties in a family of isostructural (3,24)-connected porous materials, MFM-112a, MFM-115a, and MFM-132a, with different linker backbone functionalization. Both MFM-112a and MFM-115a show excellent CH4 uptakes of 236 and 256 cm3 (STP) cm–3 (v/v) at 80 bar and room temperature, respectively. Significantly, MFM-115a displays an exceptionally high deliverable CH4 capacity of 208 v/v between 5 and 80 bar at room temperature, making it among the best performing metal–organic frameworks for CH4 storage. We also synthesized the partially deuterated versions of the above materials and applied solid-state 2H NMR spectroscopy to show that these three frameworks contain molecular rotors that exhibit motion in fast, medium, and slow regimes, respectively. In situ neutron powder diffraction studies on the binding sites for CD4 within MFM-132a and MFM-115a reveal that the primary binding site is located within the small pocket enclosed by the [(Cu2)3(isophthalate)3] window and three anthracene/phenyl panels. The open Cu(II) sites are the secondary/tertiary adsorption sites in these structures. Thus, we obtained direct experimental evidence showing that a tight cavity can generate a stronger binding affinity to gas molecules than open metal sites. Solid-state 2H NMR spectroscopy and neutron diffraction studies reveal that it is the combination of optimal molecular dynamics, pore geometry and size, and favorable binding sites that leads to the exceptional and different methane uptakes in these materials.

Yan Y. , Kolokolov D.I. , da Silva I. , Stepanov A.G. , Blake A.J. , Dailly A. , Manuel P. , Tang C.C. , Yang S. , Schröder M.
Porous Metal–Organic Polyhedral Frameworks with Optimal Molecular Dynamics and Pore Geometry for Methane Storage

Journal of the American Chemical Society. 2017. V.139. N38. P.13349-13360. DOI: 10.1021/jacs.7b05453 WOS Scopus РИНЦ AN PMID OpenAlex

Full text from publisher

Submitted:	May 26, 2017
Published online:	Sep 19, 2017
Published print:	Sep 27, 2017

Web of science:	WOS:000412043000019
Scopus:	2-s2.0-85030112744
Elibrary:	31100680
Chemical Abstracts:	2017:1275250
PMID:	28772068
OpenAlex:	W2743450242

DB	Citing
Web of science	91
Scopus	98
Elibrary	88
OpenAlex	106