Understanding and predicting the behavior of water, especially in contact with various surfaces, is a scientific challenge. Molecular-level understanding of hydrophobic effects and their macroscopic consequences, in particular, is critical to many applications. Macroscopically, a surface is classified as hydrophilic or hydrophobic depending on the contact angle formed by a water droplet. Because hydrophobic surfaces tend to cause water slip whereas hydrophilic ones do not, the former surfaces can yield self-cleaning garments and ice-repellent materials whereas the latter cannot. The results presented herein suggest that this dichotomy might be purely coincidental. Our simulation results demonstrate that hydrophilic surfaces can show features typically associated with hydrophobicity, namely liquid water slip. Further analysis provides details on the molecular mechanism responsible for this surprising result.

Summary: Distribution of alkanes and water in organic pores of shale, referred to as kerogen, is essential information required for the estimation of shale-reservoir oil and gas in place, adsorption of hydrocarbon, and fate of hydraulic-fracture water. A practical modeling approach is presented for the proper description of the kerogen pore systems with different mixed wettability, surface roughness, tortuous paths, and material disorder. Three kerogen models—activated kerogen, kerogen free of activated sites, and graphite-slit pore—with proper surface-oxidized functional groups and high-temperature and pressure maturation are constructed by simulation. Distribution of octane and water in the organic pores of these models is predicted by molecular dynamics (MD) simulation. The results from our studies underscore the need for accurate characterization of kerogen pore systems in terms of the pore morphology, level of surface activation, and pore size. The improved kerogen models constructed to structurally resemble real organic materials have the potential to enable a better understanding of the placement, distribution, and trapping mechanisms of hydraulic-fracture water in shales. We demonstrate that depending on the maturity of the kerogen within organic-rich shales, organic pore systems may have mixed-wet characteristics and may create opportunities for water entrapment. The differences in the uptake of water are shown to be a function of the existence of oxygenated functional groups. In addition, the adsorption characteristics of alkanes in pores characterized by surface roughness are shown to be significantly different from those observed in the graphite-slit pore model. Our results indicate that careful consideration of the pore morphology is merited when estimating hydrocarbons in place with the Langmuir monolayer-adsorption theory.

The importance of including the polarizability of both water and graphene in molecular dynamics simulations of the water/graphene system was quantified. A thin film of either rigid single point charge extended (SPC/E) water or polarizable simple 4-site water model with Drude polarizability (SWM4_DP) water on non-polarizable and polarizable graphene surfaces was simulated. The graphene surface was either maintained neutral or charged, positively and negatively. The results suggest that SPC/E and SWM4_DP water models yield very similar predictions for the water structural properties on neutral non-polarizable graphene, although they yield slightly different dynamical properties of interfacial water on neutral non-polarizable graphene. More pronounced were the differences obtained when graphene was modeled with a polarizable force field. In particular, the polarizability of graphene was found to enhance the number of interfacial SWM4_DP water molecules pointing one of their OH bonds towards the neutral surface. Despite this structural difference, the dynamical properties predicted for the interfacial SWM4_DP water were found to be independent on polarizability as long as the polarizability of a carbon atom is smaller than α = 0.878 Å. On charged graphene surfaces, the effect of polarizability of graphene on structural properties and some dynamical properties of SWM4_DP water is negligible because electrostatic forces due to surface charge dominate polarization forces, as expected. For all cases, our results suggest that the hydrogen bond network is insensitive to the polarizability of both water and graphene. Understanding how these effects will determine the accumulation of ions near neutral or charged graphene could have important implications for applications in the fields of energy storage and water desalination.