Anomalous Stability of Two-Dimensional Ice Confined in Hydrophobic Nanopores

The freezing of water mostly proceeds via heterogeneous ice nucleation, a process in which an effective nucleation medium not only expedites ice crystallization but also may effectively direct the polymorph selection of ice. Here, we show that water confined within a hydrophobic slit nanopore exhibits a freezing behavior strongly distinguished from its bulk counterpart. Such a difference is reflected by a strong, non-monotonic pore-size dependence of freezing temperature but, more surprisingly, by an unexpected stacking ordering of crystallized two-dimensional ice containing just a few ice layers. In particular, confined trilayer ice is found to exclusively crystallize into a well-ordered, hexagonal stacking sequence despite the fact that nanopore exerts no explicit constraint on stacking order. The absence of cubic stacking sequence is found to be originated from the intrinsically lower thermodynamic stability of cubic ice over hexagonal ice at the interface, which contrasts sharply the nearly degenerated stability of bulk hexagonal and cubic ices. Detailed examination clearly reveals that the divergence is attributed to the inherent difference between the two ice polymorphs in their surface phonon modes, which is further found to generically occur at both hydrophobic and hydrophilic surfaces.