Theoretical and experimental investigation of morphology and temperature effects on adsorption of organic vapors in single-walled carbon nanotubes

Hexane adsorption on single-walled carbon nanotube (SWNT) bundles is studied by both simulation and experimentally using a previously developed computer-aided methodology, which employed a smaller physisorbed probe molecule, nitrogen, to explore the porosity of nanotube samples. Configurational-bias grand canonical Monte Carlo simulation of hexane adsorption on localized sites of the bundles is carried out to predict adsorption on their external surface and in their internal sites. These localized isotherms are then combined into a global isotherm for a given sample by using knowledge of its tube-diameter distribution and structural parameters, such as the fraction of open-ended nanotubes and the external surface area of bundles in samples, which have been independently determined from the standard nitrogen adsorption isotherm. The near-perfect replication of experimental isotherms demonstrates the validity of our method for structural characterization of SWNT samples. The effect of temperature on adsorption is also studied and the simulation results are extrapolated to predict the limiting hexane adsorption capacity of the samples. The similarity between the hexane adsorption isotherms and those of other organic molecules demonstrates that the adsorption mechanisms explored here are not specific to hexane, and that the proposed methodology can be potentially applicable to other sorbates with equal success.