Enhancing Hydrogen Cluster Storage in Clathrate Hydrates via Defect-Mediated Lattice Engineering

Can we create even more “plenty of room at the bottom” of the confined nanospaces in clathrate hydrates by tuning the complex interactions between the host water frameworks and guest molecules? Because the lattice of the clathrate hydrate is stabilized by van der Waals forces between the host and guest, irradiating the lattice of the clathrate hydrate with energetic particles is anticipated to introduce artificial defects on the host water molecules, resulting in creating a better occupation of guest molecules. Here, we explored the effects of proton irradiation on the intermolecular hydrogen and intramolecular polar covalent bonds in the host frameworks of THF hydrates. The distinct roles of the secondary guest molecules in the lattice elongation of the proton irradiated THF hydrates were examined experimentally. Conclusively, multiple occupations of H₂ in small cages was observed at moderate pressure and temperature conditions following H₂ reloading of the lattice elongated THF hydrate.