Effects of Layer-Charge Distribution of 2:1 Clay Minerals on Methane Hydrate Formation: A Molecular Dynamics Simulation Study

Molecular dynamics simulations were used to investigate the effects of the external surface of a 2:1 clay mineral with different charge amounts and charge locations on CH₄ hydrate formation. The results showed that 5¹², 5¹²6², 5¹²6³, and 5¹²6⁴ were formed away from the clay mineral surface. The surface of the clay mineral with high- and low-charge layers was occupied by Na⁺ to form various distributions of outer- and inner-sphere hydration structures, respectively. The adsorbed Na⁺ on the high-charge layer surface reduced the H₂O activity by disturbing the hydrogen bond network, resulting in low tetrahedral arrangement of H₂O molecules near the layer surface, which inhibited CH₄ hydrate formation. However, more CH₄ molecules were adsorbed onto the vacancy in the Si-O rings of a neutral-charge layer to form semicage structures. Thus, the order parameter of H₂O molecules near this surface indicated that the arrangement of H₂O molecules resulted in a more optimal tetrahedral structure for CH₄ hydrate formation than that near the negatively charged layer surface. Different nucleation mechanisms of the CH₄ hydrate on external surfaces of clay mineral models were observed. For clay minerals with negatively charged layers (i.e., high and low charge), the homogeneous nucleation of the CH₄ hydrate occurred away from the surface. For a clay mineral with a neutral-charge layer, the CH₄ hydrate could nucleate either in the bulk-like solution homogeneously or at the clay mineral-H₂O interface heterogeneously.