Observation of interstitial molecular hydrogen in clathrate hydrates

R. Gary Grim; Brian C. Barnes; Patrick G. Lafond; Winfred A. Kockelmann; David A. Keen; Alan K. Soper; Masaki Hiratsuka; Kenji Yasuoka; Carolyn A. Koh; Amadeu K. Sum

doi:10.1002/anie.201406546

Observation of interstitial molecular hydrogen in clathrate hydrates

R. Gary Grim, Brian C. Barnes, Patrick G. Lafond, Winfred A. Kockelmann, David A. Keen, Alan K. Soper, Masaki Hiratsuka, Kenji Yasuoka, Carolyn A. Koh, Amadeu K. Sum

Department of Mechanical Engineering

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

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+H₂+H₂O hydrate system, now suggest that H₂ 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, H₂ is found within the shared heptagonal faces of the large (4³5⁹6²7³) cage and in cavities formed from the disruption of smaller (4⁴5⁴) water cages. The ability of H₂ to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H₂ 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. Breaking the boundaries: In the presence of molecular hydrogen, interstitial occupancy is observed in the type VI clathrate hydrate (see picture; tBuNH₂ in interstices (red) with H₂ (green)). This observation revises the definition of clathrate hydrate guest occupancy that assumes all guests are contained within the interior of the host water lattice.

Original language	English
Pages (from-to)	10710-10713
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	40
DOIs	https://doi.org/10.1002/anie.201406546
Publication status	Published - 2014 Sept 26

Keywords

Raman spectroscopy
density functional calculations
inclusion compounds
molecular dynamics
neutron diffraction

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.201406546

Cite this

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title = "Observation of interstitial molecular hydrogen in clathrate hydrates",

abstract = "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+H2+H2O hydrate system, now suggest that H2 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, H2 is found within the shared heptagonal faces of the large (43596273) cage and in cavities formed from the disruption of smaller (4454) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 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. Breaking the boundaries: In the presence of molecular hydrogen, interstitial occupancy is observed in the type VI clathrate hydrate (see picture; tBuNH2 in interstices (red) with H2 (green)). This observation revises the definition of clathrate hydrate guest occupancy that assumes all guests are contained within the interior of the host water lattice.",

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AU - Grim, R. Gary

AU - Barnes, Brian C.

AU - Lafond, Patrick G.

AU - Kockelmann, Winfred A.

AU - Keen, David A.

AU - Soper, Alan K.

AU - Hiratsuka, Masaki

AU - Yasuoka, Kenji

AU - Koh, Carolyn A.

AU - Sum, Amadeu K.

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AB - 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+H2+H2O hydrate system, now suggest that H2 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, H2 is found within the shared heptagonal faces of the large (43596273) cage and in cavities formed from the disruption of smaller (4454) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 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. Breaking the boundaries: In the presence of molecular hydrogen, interstitial occupancy is observed in the type VI clathrate hydrate (see picture; tBuNH2 in interstices (red) with H2 (green)). This observation revises the definition of clathrate hydrate guest occupancy that assumes all guests are contained within the interior of the host water lattice.

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KW - neutron diffraction

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Observation of interstitial molecular hydrogen in clathrate hydrates

Abstract

Keywords

ASJC Scopus subject areas

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