Abstract
A class of high-surface-area carbon hypothetical structures has been investigated that goes beyond the traditional model of parallel graphene sheets hosting layers of physisorbed hydrogen in slit-shaped pores of variable width. The investigation focuses on structures with locally planar units (unbounded or bounded fragments of graphene sheets), and variable ratios of in-plane to edge atoms. Adsorption of molecular hydrogen on these structures was studied by performing grand canonical Monte Carlo simulations with appropriately chosen adsorbent-adsorbate interaction potentials. The interaction models were tested by comparing simulated adsorption isotherms with experimental isotherms on a high-performance activated carbon with well-defined pore structure (approximately bimodal pore-size distribution), and remarkable agreement between computed and experimental isotherms was obtained, both for gravimetric excess adsorption and for gravimetric storage capacity. From this analysis and the simulations performed on the new structures, a rich spectrum of relationships between structural characteristics of carbons and ensuing hydrogen adsorption (structure-function relationships) emerges: (i) Storage capacities higher than in slit-shaped pores can be obtained by fragmentation/truncation of graphene sheets, which creates surface areas exceeding of 2600 m2/g, the maximum surface area for infinite graphene sheets, carried mainly by edge sites; we call the resulting structures open carbon frameworks (OCF). (ii) For OCFs with a ratio of in-plane to edge sites ≈1 and surface areas 3800-6500 m2/g, we found record maximum excess adsorption of 75-85 g of H2/kg of C at 77 K and record storage capacity of 100-260 g of H2/kg of C at 77 K and 100 bar. (iii) The adsorption in structures having large specific surface area built from small polycyclic aromatic hydrocarbons cannot be further increased because their energy of adsorption is low. (iv) Additional increase of hydrogen uptake could potentially be achieved by chemical substitution and/or intercalation of OCF structures, in order to increase the energy of adsorption. We conclude that OCF structures, if synthesized, will give hydrogen uptake at the level required for mobile applications. The conclusions define the physical limits of hydrogen adsorption in carbon-based porous structures