Structural and dynamical properties of aqueous NaCl brines confined in kaolinite nanopores

Quantifying thermodynamics, structural, and dynamical properties of brine confined in clay pores is critical for a variety of geo-energy applications, including underground hydrogen storage (UHS) and carbon capture and sequestration (CCS). Atomistic molecular dynamics simulations are applied here to study aqueous NaCl brines within 10-& Aring; kaolinite slit pores. NaCl concentrations are chosen at 5, 10, 12.5, and 15 wt. %, all below the solubility limit and high enough to provide statistically relevant information. The distribution of the ions within the nanopores is found not to be homogeneous. Explicitly, Na+ cations, preferentially attracted to the siloxane surface, accumulate in regions with low water density, whereas Cl- anions, attracted to the gibbsite surface of kaolinite, are found within the hydration layers. Confinement affects the properties of ions, with ion pairing being more pronounced within the pore than in bulk aqueous solutions at similar temperatures, pressures, and compositions. Conversely, the ions affect the properties of confined water. For example, the lifetime of water-water hydrogen bonds in confinement is shortened within the hydration shells; increasing salinity from 5 to 12.5 wt. % reduces the likelihood of water density fluctuations near the kaolinite surfaces, although when the NaCl concentration rises from 12.5 to 15 wt. %, Cl- anions enhance the likelihood of density fluctuations for the hydration layer near the gibbsite surface. The simulated molecular trajectories are studied further to extract diffusion coefficients. While confinement in the kaolinite nanopore reduces the mobility of all species, non-monotonic trends are observed as a function of salt concentration. The trends seem associated with the likelihood of ion pairing. Furthermore, the diffusion coefficients for the cations are predicted to be higher than those for the anions, which is contrary to what is typically observed in bulk brines. Because density fluctuations are correlated with properties such as the solubility of gases in confined water, our observations may have important implications for geo-energy applications such as UHS and CCS.