Liquid Water Confined in Cellulose with Variable Interfacial Hydrophilicity

Abstract

Abstract We investigate liquid water confined within nanoscale cellulose slabs by means of molecular dynamics simulations. Depending on the construction of the cellulose–water interface, two different surface structures with distinct levels of hydrophilicity are exposed to the water. The different philicities are reflected in the response of the water phase to this geometric confinement, both in terms of the density profile and in the strength of the aqueous hydrogen bonding network. At the smooth surface cut along the (010) axis of the cellulose crystal, water shows typical properties of a hydrophilic confinement: the density shows fluctuations that disappear further away from the wall, the water molecules orient themselves and the coordination numbers increases at the interface. As a consequence, the water becomes “harder” at the interface, with a considerably increased local ordering. At the zigzag-shaped surface along the (111) axis, the degree of hydrophilicity is reduced, and only small effects can be seen: the density shows weak fluctuations, and the orientation of the water molecules is closer to that of bulk water than to the smooth surface. The local coordination numbers remains constant over the whole confinement. Our work shows that the nature of the exposed cellulose interface has a strong influence on how the structure of adjacent water is modified. The different ways of surface construction yield distinct degrees of hydrophilicity and spatial accessibility regarding the hydrogen bond network, resulting in a notably different interfacial water structure.