Isolation of pristine MXene from Nb4AlC3 MAX phase: a first-principles study

Synthesis of pristine MXene sheets from MAX phase is one of the foremost challenges in getting a complete understanding of the properties of this new technologically important 2D-material. Efforts to exfoliate Nb4AlC3 MAX phase always lead to Nb4C3 MXene sheets, which are functionalized and have several Al atoms attached. Using the first-principles calculations, we perform an intensive study on the chemical transformation of MAX phase into MXene sheets by inserting HF, alkali atoms and LiF in Nb4AlC3 MAX phase. Calculated bond-dissociation energy (BDE) shows that the presence of HF in MAX phase always results in functionalized MXene, as the binding of H with MXene is quite strong while that with F is weak. Insertion of alkali atoms does not facilitate pristine MXene isolation due to the presence of chemical bonds of almost equal strength. In contrast, weak Li-MXene and strong Li-F bonding in Nb4AlC3 with LiF ensured strong anisotropy in BDE, which will result in the dissociation of the Li-MXene bond. Ab initio molecular dynamics calculations capture these features and show that at 500-650 K, the Li-MXene bond indeed breaks leaving a pristine MXene sheet behind. The approach and insights developed here for chemical exfoliation of layered materials bonded by chemical bonds instead of van der Waals can promote their experimental realization.