Electrocatalytic Properties of Oxygen-Deficient Perovskites Ca₃Fe_3–xMn_xO₈ (x = 1–2) for the Hydrogen Evolution Reaction

We have demonstrated a systematic trend in the electrocatalytic activity for the hydrogen evolution reaction (HER) and its correlations with transition-metal type, structural order, and electrical conductivity. The materials studied in this work, Ca3FeMn2O8 (CaFe1/3Mn2/3O3–1/3), Ca3Fe1.5Mn1.5O8, and Ca3Fe2MnO8, belong to the family of oxygen-deficient perovskites and show a gradual increase in the ordering of oxygen vacancies. Ca3FeMn2O8 (CaFe1/3Mn2/3O3–1/3) contains randomly distributed oxygen vacancies, which begin to order in Ca3Fe1.5Mn1.5O8, and are fully ordered in Ca3Fe2MnO8. The gradual increase in the structural order is associated with a systematic enhancement of the electrocatalytic activity for HER in acidic conditions, Ca3FeMn2O8 < Ca3Fe1.5Mn1.5O8 < Ca3Fe2MnO8. While the improvement of the HER activity is also associated with an increase in the Fe content, we have shown that the type of structural order plays a more important role. We demonstrated this effect by control experiments on an analogous material where all Mn was substituted by Fe, leading to a different type of structural order and showing an inferior HER activity compared to the above three materials. Furthermore, electrical conductivity studies in a wide range of temperatures, 25–800 °C, indicate that the trend in the electrical conductivity is the same as that of the HER activity. These findings reveal several important structure–property relationships and highlight the importance of synergistic effects in enhancing the electrocatalytic properties.