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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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Journal ArticleDOI

Structure and Density Comparison of Noble Gas Hydrates Encapsulating Xenon, Krypton and Argon.

TL;DR: It was revealed that host cage size of these hydrates changed depending on type of guest molecules even though their unit-cell parameters were the same, which may give insight into further understanding of the thermodynamic stability and physical properties of gas hydrate encapsulating small guests.
Journal ArticleDOI

Decomposition kinetics and recycle of binary hydrogen‐tetrahydrofuran clathrate hydrate

TL;DR: In this paper, the formation and decomposition of H 2 clathrate hydrates were investigated with a pressure decay method at temperatures from 265.1 to 273.2 K, at initial pressures from 3.1-8.0 MPa, and at stoichiometric THF hydrate concentrations for particle sizes between 250 and 1000 μm.
Journal ArticleDOI

Molecular Insights into Guest and Composition Dependence of Mixed Hydrate Nucleation

TL;DR: In this paper, a large-scale multicomponent crystals, for which natural gas hydrates are important examples, have drawn considerable attention because of their scientific and industrial importance.
Journal ArticleDOI

Experimental and theoretical analysis of the rotational Raman spectrum of hydrogen molecules in clathrate hydrates

TL;DR: The quantitative agreement between theory and experiment obtained in some cases clarifies the importance of the choice of the interaction potential, and of the proton disorder in the clathrate crystal.
References
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Journal ArticleDOI

Hydrogen clusters in clathrate hydrate.

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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