First-principles study of MXene properties with varying hydrofluoric acid concentration.

With varying hydrofluoric acid (HF) concentrations under three etching conditions, we presented a comparative study of the effects of both the ordered and randomly ternary mixed terminated TiCT surfaces with a wide variation of O/OH/F stoichiometry on the thermodynamic stability and electronic properties. Regardless of the HF concentration, an OH-rich surface is found to be thermodynamically stable and the electrical conductivity of TiCT is substantially affected by the OH concentration. The charge density difference and electron localization function demonstrated a significant electron localization at the hydroxyl group on the O/OH/F mixed terminated surface, which could yield a locally induced dipole on the surface that renders favorable reaction sites on the functionalized surface. In addition, a large tunability in the work function (ΔΦ ∼ 3.5 eV) is predicted for TiCT. These findings provide a pathway for strategically tuning the electronic and structural properties of TiC MXenes etched with HF.