Characterizing Structure-Dependent TiS₂/Water Interfaces Using Deep-Neural-Network-Assisted Molecular Dynamics

As a promising layered electrode material, TiS2-based capacitive deionization (CDI) devices for water desalination have attracted significant attention. However, TiS2/H2O interfacial features, potentially important for device optimization, remain unidentified. Using Deep Potential Molecular Dynamics (DPMD), we characterized distinct aqueous interfaces introduced by four TiS2 terminations expected to be present as water intercalates into TiS2, namely, Armchair, Zigzag, Zigzag-L, and Zigzag-R. First, we assessed important representative physical properties of the system to validate the deep potentials (DPs). DPMD simulations agree well with experiments and first-principles simulations, suggesting the DPs are accurate and reliable. Subsequent simulations of these TiS2/water interfaces revealed how TiS2 surface termination influences the structure of interfacial water. This effect is most evident in the first and second water layers close to the TiS2 surface, and more pronounced when spontaneous dissociative adsorption of water occurs. The extent of water dissociation on each surface was evaluated using enhanced sampling. Zigzag-L is the only interface where proton transfer from adsorbed water to TiS2 surface S atoms is thermodynamically and kinetically favored. The coexistence of surface four-fold-coordinated Ti (Ti4c) and one-fold-coordinated S (S1c) is found to be essential to making proton transfer feasible on the Zigzag-L surface. Furthermore, remaining unprotonated S1c atoms can act as good proton acceptors after water dissociation. Thus, TiS2 with Zigzag-L termination may be a surface to avoid in CDI device construction, given that pH fluctuations adversely affect performance. This work provides new understanding of TiS2/H2O interfacial features that could aid future design and optimization of TiS2-based CDI devices for water desalination.