Molecular-Level Insights into Unique Behavior of Water Molecules Confined in the Heterojunction between One- and Two-Dimensional Nanochannels

With the increasing importance of nanoconfined water in various heterostructures, it is quite essential to clarify the influence of nanoconfinement on the unique properties of water molecules in the pivotal heterojunction. In this work, we reported a series of classical molecular dynamics (MD) simulations to explore nanoconfined water in the subnanometer-sized and nanometer-sized heterostructures by adjusting one-dimensional (1-D) carbon nanotubes with different diameters and two-dimensional (2-D) graphene sheets with different interlayer distances. Our simulation results demonstrated that water molecules in the 1-D/2-D heterojunction show an obvious structural rearrangement associated with the remarkable breaking and formation of hydrogen bonds (HBs), and such rearrangements in the subnanometer-sized systems are much more pronounced than those in the nanometer-sized ones. When water molecules in the 1-D/2-D heterojunctions migrate from 2-D to 1-D confinements, the ordered multi-layer structure in the 2-D confinement are completely destroyed and then transform into different circular HB networks near the nanotube orifice for better connecting to the single-file or helical HB network in the 1-D nanotubes. Furthermore, water molecules in the 1-D/2-D heterojunctions can form stronger HBs with those water molecules further away from the 1-D confinement, leading to an asymmetrical orientational distribution near the orifice. More importantly, our comparison results revealed that the 1-D confinement plays a more important role than the 2-D confinement in determining both the structures and dynamics of water molecules in the 1-D/2-D heterojunction.