Differences in the adsorption and diffusion behaviour of water and non-polar gases in nanoporous carbon: role of cooperative effects of pore confinement and hydrogen bonding

AbstractWe investigate the effect of pore confinement and molecular geometry on the adsorption and self-diffusion of H2O, CO2, Ar, CH4, C3H6, SF6 and C5H12, in a realistic model of nanoporous silicon carbide derived carbon (SiC-DC), constructed using hybrid reverse Monte Carlo simulation. Adsorption isotherms, adsorbate–adsorbate and adsorbate–adsorbent contributions to the isosteric heat of adsorption are determined to study the effect of pore confinement, microporosity and molecular geometry on adsorption of these gases. We describe the cooperative effect of pore confinement and hydrogen bonding on the formation of water clusters and anomalous adsorption behaviour of water compared with non-polar gases. We find that, in contrast to literature results based on the slit-pore model, pore-filling does not occur below the saturation pressure in hydrophobic amorphous carbon materials such as SiC-DC and activated carbon fibre. We also compare self-diffusivities and activation energy barriers of water and non-polar gases in the microporous structure of SiC-DC to identify underlying correlations with molecular properties. We demonstrate that the self-diffusivity of water deviates considerably from the correlation between diffusivity and molecular kinetic diameter observed for non-polar gases. This is attributed to the reduced diffusivity of water, and its relatively large energy barrier at high loadings despite its small kinetic diameter, which is due to the blocking effect of water clusters at pore entries.Keywords:: activation energy barriermolecular dynamicsself-diffusionwater cluster AcknowledgementsThis research was undertaken with the assistance of the computational resources provided at the NCI Facility systems at the Australian National University (ANU), through the National Computational Merit Allocation Scheme supported by the Australian Government.Additional informationFundingFinancial support from Australian Research Council (ARC) under the Discovery Scheme is gratefully acknowledged.