Predicted Surface Composition and Thermodynamic Stability of MXenes in Solution

First-principles calculations are used to compare the binding energies of O, OH, and F on two-dimensional, metal carbide and nitride, or MXene, surfaces in order to predict the dependence of the thermodynamic stability of these compounds on their chemical composition. Solvation effects are implicitly included in the calculations to reproduce experimental conditions as closely as possible. The results indicate that all MXene surfaces are saturated with oxygen when exposed to H₂O/HF solutions at low hydrogen chemical potential, μ_H, and that Sc-based MXenes can also be fluorinated in solutions of higherμ_H. After investigating the thermodynamic stability of all 54 MXene compounds M_n+1X_nO₂ (M = Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta; X = C, N; n = 1, 2, 3), 38 are predicted to have formation energies below 200 meV/atom. Of these, six are predicted to have formation energies below 100 meV/atom, only one of which has been synthesized. Sc-based MXenes are found to be highly stable when their surfaces are terminated with F, which also results in the easiest exfoliation to produce freestanding single layers.