Accurate prediction of oxygen vacancy concentration with disordered A-site cations in high-entropy perovskite oxides

Entropic stabilized ABO 3 perovskite oxides promise many applications, including the two-step solar thermochemical hydrogen (STCH) production. Using binary and quaternary A-site mixed AFeO 3 as a model system, we reveal that as more cation types, especially above four, are mixed on the A-site, the cell lattice becomes more cubic-like but the local Fe–O octahedrons are more distorted. By comparing four different Density Functional Theory-informed statistical models with experiments, we show that the oxygen vacancy formation energies ( E_V^f ) distribution and the vacancy interactions must be considered to predict the oxygen non-stoichiometry ( δ ) accurately. For STCH applications, the E_V^f distribution, including both the average and the spread, can be optimized jointly to improve Δ δ (difference of δ between the two-step conditions) in some hydrogen production levels. This model can be used to predict the range of water splitting that can be thermodynamically improved by mixing cations in AFeO 3 perovskites.