Tuning the Spin State in LaCoO₃ Thin Films for Enhanced High-Temperature Oxygen Electrocatalysis

The slow kinetics of oxygen surface exchange hinders the efficiency of high-temperature oxygen electrocatalytic devices such as solid oxide fuel cells and oxygen separation membranes. Systematic investigations of material properties that link to catalytic activity can aid in the rational design of highly active cathode materials. Here, we explore LaCoO₃ thin films as a model system for tuning catalytic activity through strain-induced changes in the Co spin state. We demonstrate that Raman spectroscopy can be used to probe the Co–O bond strength at different temperatures to determine the relative spin occupancies of LaCoO₃. We find that strain can be used to reduce the spin transition temperature and promote the occupation of higher spin states that weaken the Co–O bond. The decrease in Co–O bond strength and increased spin moment of the thin films result in significant enhancements of the oxygen surface exchange kinetics by up to 2 orders of magnitude.