Upper storage-capacity limit and multiple occupancy phenomena in Hhydroquinone clathrates using Monte Carlo and DFT simulations.

The upper hydrogen-storage capacity limit of the β-hydroquinone clathrate has been investigated using hybrid Grand-Canonical Monte Carlo/Molecular Dynamics simulations, for temperatures ranging from 77 K to 300 K. The evolution with pressure of the cage occupancies has been monitored in detail, describing the progressive nature of the uptake process. It is found that the storage capacity of the pure β-HQ + H clathrate could reach 0.6 wt% (weight percentage) only for pressures above 1400 bar, at ambient temperature. The enhancement of the storage capacities by the multiple occupancy phenomenom was accordingly shown to be very limited by the need for extreme conditions. Following this observation, an unmodified version of the van der Waals & Platteeuw theory was applied allowing for the prediction of experimentally accessible formation pressures. Density functional theory calculations were addittionnaly performed to comprehensively characterize the hydrogen diffusion process within the clathrate crystalline structure, considering different occupancy scenarios.