Abstract
Heterostructured oxide interfaces created by decorating Ruddlesden-Popper phases (A2BO4) or perovskites on perovskites have shown not only pronounced cation segregation at the interface and in the A2BO4 structure but also much enhanced kinetics for oxygen electrocatalysis at elevated temperatures. In this study, we report and compare the time-dependent surface exchange kinetics and stability of (La0.5Sr0.5)2CoO4±δ-decorated (LSC214) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF113) and La0.8Sr0.2CoO3-δ (LSC113) thin films. While LSC214 decoration on LSC113 greatly reduced the degradation in the surface exchange kinetics as a function of time relative to LSC113, LSCF113 with LSC214 coverage showed comparable surface exchange kinetics and stability to LSCF113. This difference can be explained by greater surface stability of LSCF113 than LSC113 under testing conditions, and that LSC214 decoration on LSC113 reduced the decomposition of LSC113 to form secondary phases that impedes oxygen exchange kinetics, and thus resulted in enhanced stability. This hypothesis is supported by the observations that annealing at 550 °C led to the formation of Sr-rich secondary particles on LSC113 while no such particles were observed on LSCF113. Density functional theory (DFT) computation provides further support, which revealed greater capacity of surface Sr segregation for LSCF113 having SrO termination than LSC113 having (La0.25Sr0.75)O termination for the experimental conditions, and lower energy gain to move Sr from LSCF113 into LSC214 relative to the LSC214-LSC113 system.