Modeling of Hydrogen Storage Utilizing Silsesquioxane Cages: Adsorption and Quasi-Dynamic Simulations of Encapsulation of H2 Molecule into Silsesquioxane Cages.

Solid-state hydrogen storage may be the only promising way for mobile applications of hydrogen energy since it is safe, quickly reversible, cost-efficient, and has a high volumetric energy density under standard conditions. Silsesquioxane and its derivatives seem well suited for solid-state hydrogen storage and have attracted many experimental and theoretical researchers. In the present work, we have systematically studied four cages of T8, T10, and T12 (D2d and D6h) for hydrogen storage including adsorption and encapsulation of hydrogen molecules. We find that silsesquioxane cages have up to about 4150 m2/g specific surface area (SSA) and 7.81 wt % for hydrogen storage. These calculated values are comparable to the highest hydrogen storage values of metal-organic frameworks, porous polymer networks, and covalent organic frameworks. In addition, we use the quasi-dynamic method to study the encapsulation of hydrogen molecules into these cages because of the timescale limitation of ab initio molecular dynamics. Thermodynamic parameters such as enthalpy and Gibbs free energy at different temperatures are calculated during the insertion processes. We find that the insertion process of a hydrogen molecule into the T12 (D6h) cage is almost energy-conserved and its energy barriers of enthalpy and free energy are moderate under standard conditions.