Methane hydrates can be preserved at ambient pressure, beyond their region of thermodynamic stability, by storing them at temperatures from 240 to 270 K. The origin of this anomalous self-preservation is the formation of an ice coating that covers the clathrate particles and prevents further loss of gas. While there have been several studies on self-preservation, the question of what is the mechanism by which ice nucleates on the decomposing clathrate hydrates has not yet been fully explained. Here, we use molecular simulations, thermodynamic analysis, and nucleation theory to investigate possible scenarios for the nucleation of ice: heterogeneous nucleation at the clathrate/vapor or clathrate/liquid interfaces and homogeneous nucleation from supercooled water. Our results indicate that clathrates cannot heterogeneously nucleate ice and that ice nucleation is due to the cooling of water at the decomposing clathrate/liquid interface, which suffices to trigger homogeneous ice nucleation. We find that the (111) face of the sII structure clathrate can bind to the (111) plane of cubic ice or the basal plane of hexagonal ice through domain matching, resulting in a weak binding that—while insufficient to promote heterogeneous ice nucleation—suffices to produce epitaxy and alignment between these crystals. We use thermodynamic relations, theory, and the contact angles of ice at the (111) sII clathrate/liquid interface to determine—for the first time—the interfacial free energy of this most favorable ice-clathrate interface, 59 ± 5 mJ/m2. We discuss the implications of our results for the feasibility of heterogeneous nucleation of gas clathrates at ice/vapor interfaces.
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