Abstract
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 Ti(3)C(2)T(x) 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 Ti(3)C(2)T(x) 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 Ti(3)C(2)T(x). These findings provide a pathway for strategically tuning the electronic and structural properties of Ti(3)C(2) MXenes etched with HF.