Surface Functionalization of 2D MXenes: Trends in Distribution, Composition, and Electronic Properties

Using a multiscale computational scheme, we study the trends in distribution and composition of the surface functional groups −O, −OH, and −F on two-dimensional (2D) transition metal carbides and nitrides (MXenes). We consider Ti₂N, Ti₄N₃, Nb₂C, Nb₄C₃, Ti₂C, and Ti₃C₂ to explore MXenes with different chemistry and different number of atomic layers. Using a combination of cluster expansion, Monte Carlo, and density functional theory methods, we study the distribution and composition of functional groups at experimentally relevant conditions. We show that mixtures of functional groups are favorable on all studied MXene surfaces. The distribution of functional groups appears to be largely independent of the type of metal, carbon, or nitrogen species and/or number of atomic layers in the MXene. We further show that some properties (e.g., the work function) strongly depend on the surface composition, while others, for example, the electric conductivity, exhibit only a weak dependence.