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A new software package, RASPA, for simulating adsorption and diffusion of molecules in flexible nanoporous materials is presented. The code implements the latest state-of-the-art algorithms for molecular dynamics and Monte Carlo (MC) in various ensembles including symplectic/measure-preserving integrators, Ewald summation, configurational-bias MC, continuous fractional component MC, reactive MC and Baker's minimisation. We show example applications of RASPA in computing coexistence properties, adsorption isotherms for single and multiple components, self- and collective diffusivities, reaction systems and visualisation. The software is released under the GNU General Public License. [ABSTRACT FROM PUBLISHER]

Diffusion of methane, ethane, propane and n-butane was studied within the micropores of several metal-organic frameworks (MOFs) of varying topologies, including the MOFs PCN-14, NU-125, NU-1100 and DUT-49. Diffusion coefficients of the pure components, as well as methane/ethane, methane/propane and methane/butane binary mixtures, were calculated using molecular dynamics simulations to understand the effect of the longer alkanes on uptake of natural gas in MOFs. The calculated self-diffusion coefficients of all four components are on the order of 10 −8 m 2 /s. The diffusion coefficients of the pure components decrease as a function of chain length in all of the MOFs studied and show different behaviour as a function of loading in different MOFs. The self-diffusivities follow the trend D PCN-14 NU-125≈NU-1100>DUT-49. By comparing the diffusion of pure methane and methane mixtures with the higher alkanes, it is observed that the diffusivity of methane is unaffected by the presence of the higher alkanes in the MOFs considered, indicating that the diffusion path of methane is not blocked by the higher alkanes present in natural gas. [ABSTRACT FROM AUTHOR]

The methane deliverable capacity of adsorbent materials is a critical performance metric that will determine the viability of using adsorbed natural gas (ANG) technology in vehicular applications. ARPA-E recently set a target deliverable capacity of 315 cc(STP)/cc that a viable adsorbent material should achieve to yield a driving range competitive with incumbent fuels. However, recent computational screening of hundreds of thousands of materials suggests that the target is unattainable. In this work, we aim to determine whether the observed limits in deliverable capacity (~200 cc(STP)/cc) are fundamental limits arising from thermodynamic or material design constraints. Our efforts focus on simulating methane adsorption isotherms in a large number of systems, resulting in a broad exploration of different combinations of spatial distributions and energetics of adsorption sites. All systems were classified into five adsorption scenarios with varying degrees of realism in the manner that adsorption sites are created and endowed with energetics. The scenarios range from methane adsorption on discrete idealized lattice sites to adsorption in metal–organic frameworks with coordinatively unsaturated sites (CUS) provided by metalated catechol groups. Our findings strongly suggest that the ARPA-E target is unattainable, although not due to thermodynamic constraints but due to material design constraints. On the other hand, we also find that the currently observed deliverable capacity limits may be moderately surpassed. For instance, incorporation of CUS in IRMOF-10 is predicted to yield a 217 cc(STP)/cc deliverable capacity. The modified material has a ~0.85 void fraction and a heat of adsorption of ~15 kJ/mol. This suggests that similar, moderate improvements over existing materials could be achieved as long as CUS incorporation still maintains a relatively large void fraction. Nonetheless, we conclude that more significant improvements in deliverable capacity will require changes in the currently proposed operation conditions. [ABSTRACT FROM AUTHOR]