Calcium-Decorated Polygon-Graphenes for Hydrogen Storage

We performed first-principles calculations to investigate hydrogen (H 2 ) storage properties of bare and calcium (Ca)-decorated polygon-graphenes, i.e., biphenylene and ψ-graphene monolayers consisting of polygons, from tetragons to octagons. In pristine forms, both biphenylene and ψ-graphene bind H 2 weakly. However, upon Ca doping, biphenylene adsorbed up to five H 2 molecules regardless of polygonal sites, whereas ψ-graphene anchored up to six and five H 2 molecules to pentagonal and heptagonal sites, respectively. In all the cases, the H 2 binding energy was ∼0.30 eV, enabling reversible room-temperature H 2 storage. The H 2 storage capacity can reach ∼6.8 and ∼4.2 wt % for Ca-decorated biphenylene and ψ-graphene, respectively. Using equilibrium thermodynamics, we showed the adsorption and desorption of H 2 at 300 and 380 K under ambient pressure, respectively. This clearly indicates that Ca-decorated 2D sp 2 carbon sheets with polygons (biphenylene, ψ-graphene) could be used as promising H 2 storage materials.