Theoretical investigation of the MXene precursors MoVAlC (0 ≤ x ≤ 4).

By first-principles total-energy calculations, we investigated the thermodynamic stability of the MAX solid solution MoVAlC in the 0 ≤ x ≤ 4 range. Results evidence that lattice parameter a increases as a function of Mo content, while the c parameter reaches its maximum expansion at x = 2.5. After that, a contraction is noticed. Mo occupies V sites randomly until the out-of-plane ordered MoVAlC alloy is formed. We employed the Defect Formation Energy (DFE) formalism to evaluate the thermodynamic stability of the alloys. Calculations show five stable compounds. At V-rich conditions and from Mo-rich to Mo-moderated conditions, the pristine VAlC MAX is stable. In the region of V-poor conditions, from Mo-rich to Mo-moderated growth conditions, the solid solutions with x = 0.5, 1, and 1.5 and the o-MAX MoVAlC are thermodynamically stable. The line profiles of the Electron Localization Function and Bader charge analysis show that the V-C interaction is mainly ionic, while the Mo-C is covalent. Also, the exfoliation energy to obtain a MXene layer is ~ 0.4 eV/Å. DFE also shows that MXenes exfoliated from the MAX phase with the same Mo content and atomic arrangement are thermodynamically stable. Our results get a deeper atomic scale understanding of the previously reported experimental evidence.