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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

Theoretical modeling of the thermodynamic properties and the phase diagram of binary gas hydrates of argon and hydrogen

TL;DR: Theoretical calculation of the thermodynamic properties and determining of equilibrium hydrate composition of binary argon+hydrogen hydrates has been performed with taking into account the concurrent cage occupation by different guest types as discussed by the authors.
Journal ArticleDOI

Cucurbiturils as promising hydrogen storage materials: a case study of cucurbit[7]uril

TL;DR: In this article, the hydrogen storage capacity of cucurbit[7]uril, as a representative of the cucurbitsuril family, at the ωB97X-D/6-31G(d,p) level of theory was investigated.
Journal ArticleDOI

Molecular-Dynamics and First-Principles Calculations of Raman Spectra and Molecular and Electronic Structure of Hydrogen Clusters in Hydrogen Clathrate Hydrate

TL;DR: In this paper, first-principles calculations are employed to understand vibrational spectroscopy and molecular and electronic structure of the encaged hydrogen molecules in hydrogen clathrate hydrate.
Journal ArticleDOI

Accelerated formation of THF-H2 clathrate hydrate in porous media.

TL;DR: Stoichiometric tetrahydrofuran-hydrogen binary clathrate hydrates with approximately 1 wt % hydrogen loading formed in the mesopores of four porous media with median pore diameters of 49, 65, 100, and 226 A at 270 K and hydrogen pressure of 65 bar.
Journal ArticleDOI

Hydrogen Sorption Efficiency of Titanium-Functionalized Mg–BN Framework

TL;DR: In this article, metal-organic framework with organic linker is replaced with BN linker namely borazocine (B4N4H8) and is functionalized with Ti, enhancing the stability and storage capacity of the framework.
References
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Journal ArticleDOI

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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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