Diffusion and adsorption of methane confined in nano-porous carbon aerogel: A combined quasi-elastic and small-angle neutron scattering study

The diffusion of methane confined in nano-porous carbon aerogel with the average pore size 48 Å and porosity ∼60% was investigated as a function of pressure at T = 298 K using quasi-elastic neutron scattering (QENS). The diffusivity of methane shows a clear effect of confinement: it is about two orders of magnitude lower than in bulk at the same thermodynamic conditions and is close to the diffusivity of liquid methane at 100 K (i.e. ∼90 K below the liquid-gas critical temperature T_C ≈ 191 K). The diffusion coefficient (D) of methane initially increases with pressure by a factor of ∼2.5 from 3.47 ± 0.41 × 10^-10 m² s^-1 at 0.482 MPa to D = 8.55 ± 0.33 × 10^-10 m² s^-1 at 2.75 MPa and starts to decrease at higher pressures. An explanation of the observed non-monotonic behavior of the diffusivity in the confined fluid is based on the results of small-angle neutron scattering experiments of the phase behavior of methane in a similar carbon aerogel sample. The initial increase of the diffusion coefficient with pressure is explained as due to progressive filling of bigger pores in which molecular mobility in the internal pore volume is less affected by the sluggish liquid-like molecular mobility in the adsorbed phase. Subsequent decrease of D, is associated with the effect of intermolecular collisions, which result in a lower total molecular mobility with pressure, as in the bulk state. The results are compared with the available QENS data on the methane diffusivity in zeolites, metal organic frameworks, and porous silica as well as with the molecular dynamics simulations of methane in nano-porous carbons and silica zeolites. © 2010 Elsevier Inc. All rights reserved.