ReaxFF molecular dynamics of graphene oxide/NaCl aqueous solution interfaces

Abstract

In this work, the interaction of NaCl aqueous solution with graphene (G), graphene oxide (GO), and graphite oxide (GTO) is studied using the ReaxFF module of Amsterdam Modeling Suite (AMS) software. We consider four models using the NaCl aqueous solution, containing a graphene sheet (G), a single sheet of GO with epoxide and hydroxyl groups on its surface, 4 layers of GO to model GTO, and a bulk NaCl solution as a reference. The structural and dynamical properties of G, GO, and GTO were quantified by analyzing the functional groups, radial distribution functions, density profiles and diffusivities of water and ions. Due to the reactive force field, the systems underwent spontaneous modification of surface functional groups during the first 750 ps after which the structure stabilizes (the energy stabilizes in less than 400 ps). Pristine graphene in contact with the NaCl solution formed hydroxyl groups on the edges, i.e., converted to partially reduced graphene oxide. The epoxy groups (O_e) on the initial GO were rather unstable, leading to a reduction of their number, however, there was an increase in the number of hydroxyl groups (O_h), mainly at the edges. The interactions of NaCl with the carbon-based sheets are rather weak, including GO and GTO which are decorated with numerous functional groups. Diffusion coefficients of water agree with the available data, but discrepancies in Na⁺ and Cl⁻ diffusivity compared to other references underscore the need for further development in the dynamic parameters of the reactive force field used. In essence, our research provides specific data previously unreported, laying a foundation for advancing water desalination system design. The study's novelty lies in its realistic approach to graphene/graphene oxide modification, comprehensive characterization, and the application of the reactive force field to explore the graphene oxide-NaCl aqueous interface, contributing to the development of a practical membrane system for water desalination.