Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

Carter, Joseph H.; Savage, Mathew; da Silva, Ivan; Johnson, Mark; Newby, Ruth; Suyetin, Mikhail; Besley, Elena; Manuel, Pascal; Rudi?, Svemir; Fitch, Andrew N.; Murray, Claire; David, William I. F.; Yang, Sihai; Schr�der, Martin

Abstract

The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.

• Journal Article Type: Article
• Acceptance Date: Jul 16, 2016
• Online Publication Date: Jul 13, 2016
• Publication Date: Jul 27, 2016
• Deposit Date: Mar 10, 2020
• Publicly Available Date: May 15, 2020
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 138
• Issue: 29
• Pages: 9119-9127
• DOI: https://doi.org/10.1021/jacs.6b01323
• Public URL: https://nottingham-repository.worktribe.com/output/4122124
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.6b01323