Single-Molecule Water Motion on h-BN and Graphene: A Paradigm Shift in Understanding the Behaviour of Water on 2D Material Interfaces

Abstract: Understanding water behaviour on 2D materials is crucial for sensing, microfluidics, and tribology. While water/graphene interactions are well studied, water on hexagonal boron nitride (h-BN) remains largely unexplored. Despite structural similarity to graphene, h-BN's slightly polar B-N bonds impart a large band gap, high thermal conductivity, and chemical stability, making it promising for electronics, lubricants, and coatings. Moreover, existing water studies often focus on multilayer water dynamics, overlooking single-molecular details. We bridge this gap by studying single-molecular water friction and diffusion on h-BN, comparing it with graphene using helium spin-echo experiments and ab initio calculations. Our findings show that water diffusion on h-BN/Ni follows a complex rotational-translational dynamic, unlike graphene. While conventional views treat water motion as discrete jumps between equivalent adsorption sites, we demonstrate that on h-BN, water molecules rotate freely around their centre of mass. Although the binding energies of water on h-BN and graphene are similar, the activation energy for water dynamics on h-BN is 2.5 times lower than on graphene, implying a much lower barrier for molecular mobility. The fundamentally different diffusion characteristics which classical models cannot capture, underscores the need to rethink how we model water on polar 2D materials. Moreover, our analysis reveals that the metal substrate strongly influences water friction, with h-BN/Ni showing a markedly lower friction than graphene/Ni, in stark contrast to the free-standing materials. These findings challenge assumptions about 2D material-water interactions, highlighting the crucial role of substrate effects in chemistry and material science and offer insights for designing next-generation microfluidic devices that require precise water mobility control.