Computational Pourbaix Diagrams for MXenes: A Key Ingredient toward Proper Theoretical Electrocatalytic Studies

Abstract

AbstractMXenes, a rather new family of 2D carbides and nitrides, have shown to be promising materials in many technological applications, particularly in electrocatalysis. The as‐synthesized MXenes exhibit a variety of surface terminations involving mixtures of O, OH, H, or F surface groups. These terminations play a crucial role in the electrocatalytic performance of these materials as these may change depending on the reaction conditions. The Pourbaix diagrams have long being used to provide the thermodynamically stable surface under certain conditions of pH and potential, U. However, experimental determination of Pourbaix diagrams may be quite challenging while first‐principles studies, considering the most likely terminations, allow deriving reliable insights. Here, Pourbaix diagrams for a series of representative MXenes are provided; the Ti2C, Ti3C2, V2C, and Mo2C MXenes, with the novelty of considering single and several double mixed terminations. The possible implications of the obtained results are discussed, especially for a proper choice of models in theoretical electrocatalysis studies, including the water splitting related hydrogen evolution reaction (HER), or the oxygen reduction reaction (ORR), but also serving as a guide to any further computational studies and also to electrocatalytic experiments.