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Observation of Interstitial Molecular Hydrogen in Clathrate Hydrates
Author(s) -
Grim R. Gary,
Barnes Brian C.,
Lafond Patrick G.,
Kockelmann Winfred A.,
Keen David A.,
Soper Alan K.,
Hiratsuka Masaki,
Yasuoka Kenji,
Koh Carolyn A.,
Sum Amadeu K.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201406546
Subject(s) - clathrate hydrate , hydrate , molecule , chemical physics , chemistry , crystallography , molecular dynamics , crystal structure , hydrogen , lattice (music) , computational chemistry , physics , organic chemistry , acoustics
The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert ‐butylamine+H 2 +H 2 O hydrate system, now suggest that H 2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H 2 is found within the shared heptagonal faces of the large (4 3 5 9 6 2 7 3 ) cage and in cavities formed from the disruption of smaller (4 4 5 4 ) water cages. The ability of H 2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H 2 in solids and reveals new insight into guest–guest and guest–host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties.

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