A Joint Theoretical And Experimental Study Of Phase Equilibria And Evolution In Pt-Doped Calcium Titanate Under Redox Conditions

Pseudoternary phase diagrams of the PtOx-CaO-TiOx system were constructed using first-principles theoretical methods to interpret experimental observations of phase formation and evolution in Pt-doped CaTiO3 made by aberration-corrected scanning transmission electron microscopy. In this system, promoted as a self-regenerative automotive exhaust-gas catalyst, Pt precipitates as metallic particles from the doped perovskite under reducing conditions and tends to redissolve under oxidizing conditions. Due to the likely influence of kinetic limitations on experimental observations, we focus on a restricted (metastable) phase diagram in which single and other unobserved oxides of Pt are intentionally excluded. Various titanate phases appear, however, and their presence helps inform the calculation of the phase diagrams, which in turn confirm that the self-regenerative effect is a consequence of thermodynamic phase stability under the specific redox environments examined.