Phase Formation, Microstructural Evolution, and Surface Performance of High-Entropy Alloys for Electrocatalysis and Corrosion Resistance: A Review

High-entropy alloys (HEAs) are a unique metallic alloy that was initially recognized for the possibility of stabilizing simple solid-solution phases through high configurational entropy. Research over the past two decades, however, has shown that their behavior is far more complex. Phase formation, microstructural evolution, and surface performance arise from the combined influence of composition, atomic interactions, processing history, and the surrounding environment. This paper reviews the connections between these aspects moving from the bulk alloy to the surface. The thermodynamic and empirical criteria utilized for prediction of phase formation and reasons behind ignoring the factors such as ordering, segregation, metastability, and processing defects are described. Further, the influence of casting, rapid solidification, coating deposition, and thin-film processing on the microstructure that will interact with catalytic or corrosive environment is reviewed. Electrocatalysis and corrosion resistance are considered as two strongly coupled surface phenomena rather than separate fields of application. Quantitative comparison of exemplary high-entropy alloy systems shows the influence of the alloying approach and surface development on the catalytic properties, surface reconstruction, selective dissolution, passive film formation, and localized corrosion. The potential of CALPHAD modeling, density functional theory, machine learning, and multi-objective optimization for a better alloy selection in the field of high-entropy alloys is reviewed as well. We identified that the success of HEA design is not only in choosing the right composition but rather in controlling the phases, defects, interfaces, and surface of the HEA.