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Tuning clathrate hydrates for hydrogen storage

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TLDR
Hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to ∼4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability.
Abstract
The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

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Citations
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Journal ArticleDOI

Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form

TL;DR: It is shown that the deformation of the host water cages of 2-propanol+CH4 hydrate can be explained by the restriction of the motion of2- Propanol within the 5(12) 6(4) host water cage, which provides a low-temperature structure due to a temperature-induced symmetry-lowering transition of clathrate hydrate.
Journal ArticleDOI

Monte Carlo study of sI hydrogen hydrates

TL;DR: In this article, the authors performed grand canonical Monte Carlo simulations to evaluate the hydrogen storage capacity of structure I (sI) hydrogen hydrates at pressures up to 500 MPa.
Journal ArticleDOI

Cage occupancies, lattice constants, and guest chemical potentials for structure II hydrogen clathrate hydrate from Gibbs ensemble Monte Carlo simulations

TL;DR: In this article, equilibrium properties of structure II hydrates of hydrogen were determined from Monte Carlo simulations in the isothermal-isobaric Gibbs ensemble, and they were described by the TIP4P/Ice and Silvera-Goldman models, respectively.
Journal ArticleDOI

Spectroscopic Identification on Cage Occupancies of Binary Gas Hydrates in the Presence of Ethanol

TL;DR: It is verified that ethanol molecules cannot inhibit hydrate formation effectively, but enhance the gas storage in the hydrate phase when a much less amount of the inhibitor than the stoichiometric concentration is used.
Journal ArticleDOI

Effect of Molecular Nitrogen on Multiple Hydrogen Occupancy in Clathrate Hydrates

TL;DR: In this article, the authors demonstrate the use of binary (LGM + N2) hydrates to capture hydrogen clusters under relatively mild conditions, even observing double H2 occupancy in small cages.
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Journal ArticleDOI

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Journal ArticleDOI

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TL;DR: High-pressure Raman, infrared, x-ray, and neutron studies show that H2 and H2O mixtures crystallize into the sII clathrate structure with an approximate H2/H2Omolar ratio of 1:2.
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