Tunable Gravimetric and Volumetric Hydrogen Storage Capacities in Polyhedral Oligomeric Silsesquioxane Frameworks

We study the hydrogen adsorption in porous frameworks composed of silsesquioxane cages linked via boron substituted aromatic structures by first-principles modeling. Such polyhedral oligomeric silsesquioxane (POSS) frameworks can be further modified by decorating them with metal atoms binding to the ring structures of the linkers. We have considered Sc- and Ti-doped frameworks which bind H<sub>2</sub> via so-called Kubas interaction between hydrogen molecules and transition metal atoms. It will be demonstrated that the maximum H<sub>2</sub> gravimetric capacity can be improved to more than 7.5 wt % by using longer linkers with more ring structures. However, the maximum H<sub>2</sub> volumetric capacity can be tuned to more than 70 g/L by varying the size of silsesquioxane cages. We are optimistic that by varying the building blocks, POSS frameworks can be modified to meet the targets for the gravimetric and volumetric capacities set by the U.S. Department of Energy.