Design principles of perovskites for solar-driven thermochemical splitting of CO.

Perovskites are attractive redox materials for thermo/electrochemical fuel synthesis. To design perovskites with balanced redox energetics for thermochemically splitting CO, the activity of lattice oxygen vacancies and stability against crystal phase changes and detrimental carbonate formation are predicted for a representative range of perovskites by electronic structure computations. Systematic trends in these materials properties when doping with selected metal cations are described in the free energy range defined for isothermal and temperature-swing redox cycles.