Insights into surface alkaline-earth segregation on the surface of La0.3Me0.7Fe0.7Cr0.3O3−δ (Me = Sr, Ca) porous electrodes for oxygen reduction reaction

Abstract Surface alkaline-earth segregation is a common problem encountered for the cathodes of solid oxide fuels cells based on perovskites (ABO3) containing alkaline-earth acceptor dopants. In this work, the porous electrodes of La0.3Me0.7Fe0.7Cr0.3O3−δ (Me = Sr, Ca) were employed as the model specimens to look into the surface segregation issue. The two electrodes were cathodically polarized by continuously testing their cathodic current polarization curves. The electrocatalytic activity of the two electrodes was examined in relation with their cathodic polarization history. Moreover, the crystal and surface structures of the cathodically polarized electrodes were analyzed. An appreciable segregation of strontium onto the surface was detected for cathodically polarized La0.3Sr0.7Fe0.7Cr0.3O3−δ electrode, leading to an obvious deceleration of disassociative adsorption of molecular oxygen on the surface and thus degradation of the electrode activity. In contrast, La0.3Ca0.7Fe0.7Cr0.3O3−δ electrode displayed nearly negligible surface calcium segregation and degradation of the electrocatalytic activity after experiencing an identical cathodic polarization history. The disparity of the two electrodes was related to their A-site compositions. This work exemplifies the importance of minimizing A-site cation size mismatch in stabilizing the crystal structure of the perovskite electrodes under cathodic polarization conditions and therefore alleviating the segregation of A-site alkaline-earth cations onto the electrode surface.