Molecular simulations of water adsorption and transport in mesopores with varying hydrophilicity arrangements

Abstract

The adsorption and transport of water in an open cylindrical mesopore with two different inner surface arrangements of hydrophilicities were examined by molecular simulations. The first model has a weak hydrophilic surface at both entrances of the pore and a stronger hydrophilic surface in the mid-section. The second pore has stronger hydrophilic surfaces at the entrances and weaker in the middle region. The simulation results show that the water adsorption isotherms obtained from Grand Canonical Monte Carlo simulations and pore filling curves acquired from Grand Canonical Molecular Dynamics simulations change depending on the arrangement of the strong and weak hydrophilic surfaces. In the first model, water condensation focuses on the mid-section forming a liquid bridge or a film, which creates a concave meniscus accelerating subsequent adsorption within the pore. Two bridges form in the entrance regions, where a cavity naturally occurs in between the films, in the second model. The different filling and emptying mechanisms clearly change the adsorption–desorption characteristics for the two pore types, but the second type generally showed faster transitions overall. Flux and meniscus analysis also reveals a circulating flow at the menisci of the interfaces within the pore. The results are expected to be valuable in understanding the effects of interior surface modification of nanopores in future applications.