Aqueous Affinity and Interfacial Dynamics of Anisotropic Buckled Black Phosphorous

The structure of black phosphorous (BP) is similar to the honeycomb arrangement of graphene, but the layered BP is found to be buckled and highly anisotropic. The buckled surface structure affects interfacial molecule mobility and plays a vital role in various nanomaterial applications. The BP is also known for wettability, droplet formation, stability, and hydrophobicity in the aqueous environment. However, there is a gap concerning the structural and dynamical behavior of water molecules, which is available in abundance for other monoatomic and polyatomic two-dimensional (2D) materials. Motivated by the technological importance, we try to bridge the gap by explaining the surface anisotropy-facilitated behavior of water molecules on bilayer BP using classical and first principles molecular dynamics (MD) simulations. From our classical MD study, we find three distinct layers of water molecules. The water layer closest to the interface is L1, followed by L2 and L3/bulk perpendicular to the BP surface. Water molecules in the L1 layer experience some structural disintegration in hydrogen bond (HB) phenomena compared to the bulk. There is a loss of HB donor–acceptor count per water molecule. The average HB count decreases because of an elevated rate of HB formation and deformation; this would affect the dynamic properties in terms of HB lifetime. Therefore, we observe the reduced lifetime of HB in the layer in close contact with BP, which again complements our finding on the diffusion coefficient of water molecules in distinct layers. Water diffuses relatively faster with diffusion coefficient 3.25 × 10–⁹ m² s–¹ in L1, followed by L2 and L3. The BP layer shows moderate hydrophobic nature. Our results also indicate the anisotropic behavior as the diffusion along the x-direction is faster than that along the y-direction. The gap in the slope of the x and y components of mean-squared displacement (MSD) complements the pinning effect in an aqueous environment. We observe blue-shifted and red-shifted libration and O-H stretching modes from the calculated power spectra for the L1 water molecules compared to the L2 and L3 molecules from first principles MD simulations. Our analysis may help understand the physical phenomena that occur during the surface wetting of the predroplet formation process observed experimentally.