PredictingAqueous and Electrochemical Stability of2D Materials from Extended Pourbaix Analyses

A key challenge for computational discovery of electrocatalytic materials is the reliable prediction of thermodynamic stability in an aqueous environment and under different electrochemical conditions. In this work, we first evaluate the electrochemical stability of more than 3000 two-dimensional (2D) materials using conventional Pourbaix diagrams (CPDs). Due to the complete neglect of thermodynamic barriers along the (often complex) reaction pathways, the vast majority of the materials are predicted to be unstable, even though some are known to be stable in practice. We then introduce an analysis based on the surface Pourbaix diagram (SPD) including “early intermediate states” that represent the first steps of the key surface passivation and dissolution reactions. The SPD framework is applied to the 2D materials MoS₂, phosphorene, and the MXene Ti₂C, all of which are predicted to be unstable by the CPD. For MoS₂, our approach reproduces the experimental pH-<i>U</i> stability window as well as the experimental desulfurization potential. For phosphorene and Ti₂C, the SPD approach is used to investigate the spontaneous degradation mechanism and the potential-dependent surface termination, respectively, again yielding good agreement with the experiments. The SPD-based stability analysis emerges as a versatile and quantitative method for prediction of stability and investigation of surface structures in electrochemical environments.