Towards First Principles-Based Prediction of Highly Accurate Electrochemical Pourbaix Diagrams

Abstract

Electrochemical potential/pH (Pourbaix) diagrams underpin many aqueous electrochemical processes and are central to the identification of stable phases of metals for processes ranging from electrocatalysis to corrosion. Even though standard DFT calculations are potentially powerful tools for the prediction of such diagrams, inherent errors in the description of transition metal (hydroxy)oxides, together with neglect of van der Waals interactions, have limited the reliability of such predictions for even the simplest pure metal bulk compounds, and corresponding predictions for more complex alloy or surface structures are even more challenging. In the present work, through synergistic use of a Hubbard U correction, a state-of-the-art dispersion correction, and a water-based bulk reference state for the calculations, these errors are systematically corrected. The approach describes the weak binding that occurs between hydroxyl-containing functional groups in certain compounds in Pourbaix diagrams, corrects f...