Towards the description of adsorption of water in slit-like pores with walls covered by molecular brushes.

Abstract

The density profiles, adsorption isotherms, and phase behavior of a water model in a slit-like pore with walls modified by pre-adsorbed tethered chain molecules have been studied in the framework of a density functional theory. Each chain is bonded to the surface by its terminal segment, and the surface density of grafted chains is the same for each wall. The model for water taken from the work of Clark et al. [Mol. Phys. 104, 3561 (2006)] reproduces successfully a bulk equation of state. The mean field approach has been used to describe the effects of attractive interactions. The chemical association effects are taken into account by using the first-order thermodynamic perturbation theory of Wertheim. We have found that the presence of molecular brushes on the pore walls has important consequences for the adsorption and phase behavior of confined water. If the brush segments do not attract water molecules strongly, the vapor-liquid coexistence envelope shrinks upon increasing brush density, but the critical temperature is weakly affected. Alteration from capillary condensation to evaporation is observed with changes in the brush density, number of segments of tethered chains, and/or chemical identity of segments. The crossover temperature is affected by all these factors. Moreover, we have shown that affinity of water to segments of tethers is an important factor determining adsorption of water vapor and the entire phase diagram.