Unveiling the key factor for the phase reconstruction and exsolved metallic particle distribution in perovskites

Abstract

To significantly increase the amount of exsolved particles, the complete phase reconstruction from simple perovskite to Ruddlesden-Popper (R-P) perovskite is greatly desirable. However, a comprehensive understanding of key parameters affecting the phase reconstruction to R-P perovskite is still unexplored. Herein, we propose the Gibbs free energy for oxygen vacancy formation in Pr_0.5(Ba/Sr)_0.5TO_3-δ (T = Mn, Fe, Co, and Ni) as the important factor in determining the type of phase reconstruction. Furthermore, using in-situ temperature & environment-controlled X-ray diffraction measurements, we report the phase diagram and optimum 'x' range required for the complete phase reconstruction to R-P perovskite in Pr_0.5Ba_0.5-xSr_xFeO_3-δ system. Among the Pr_0.5Ba_0.5-xSr_xFeO_3-δ, (Pr_0.5Ba_0.2Sr_0.3)₂FeO_4+δ - Fe metal demonstrates the smallest size of exsolved Fe metal particles when the phase reconstruction occurs under reducing condition. The exsolved nano-Fe metal particles exhibit high particle density and are well-distributed on the perovskite surface, showing great catalytic activity in fuel cell and syngas production.