Concentration-dependent self-diffusion of liquids in nanopores: a nuclear magnetic resonance study

Nuclear magnetic resonance has been applied to study the details of molecular motion of low-molecular-weight polar and nonpolar organic liquids in nanoporous silicon crystals of straight cylindrical pore morphology at different pore loadings. Effective self-diffusion coefficients as obtained using the pulsed field gradient nuclear magnetic resonance method were found to pass through a maximum with increasing concentration for all liquids under study. Taking account of a concentration-dependent coexistence of capillary condensed, adsorbed and gaseous phases a generalized model for the effective self-diffusion coefficient was developed and shown to satisfactorily explain the experimental results. An explicit use of the adsorption isotherm properties within the model extends its applicability to the mesoporous range and highlights the role of surface interaction for the transport of molecules in small pores. The problem of surface diffusion and diffusion of multilayered molecules is also addressed.