Metal nanoparticles exsolved and anchored at the parent perovskite oxide surfaces can greatly enhance the activity and antisintering stability for high-temperature (electro-) chemical catalytic reactions. While exsolution of nanoparticles triggered by using conventional high-temperature thermal reduction suffers from slow kinetics, using an electrochemical driving force can promote the exsolution rate. However, a quantitative correlation between the applied electrochemical driving force and the spatial density of exsolved nanoparticles remains unknown. In this work, we use a specially designed electrochemical device to induce a spatially graded voltage in a La0.43Ca0.37Ti0.94Ni0.06O3-δ electrode, in order to systematically investigate the effect of electrochemical switching on exsolution. With increasing driving force, which leads to decreasing oxygen chemical potential, the density of nanoparticles was observed to increase dramatically, while the average particle size remained roughly constant. We further identified oxygen vacancy pairs or clusters as the preferential nucleation sites for exsolution. Our work provided a high-throughput platform for the systematic study of exsolution of perovskite oxides targeted for fuel electrode materials with improved electrocatalytic performance and stability.
Keywords: electrochemically driven exsolution; nonstoichiometry gradient; oxygen exchange kinetics; perovskite oxide; solid oxide cells.