Structural and morphological alterations induced by cobalt substitution in LaMnO3 perovskites

The chemical composition of a LaMnO3 perovskite was modified sequentially by an improved sol–gel method to include cobalt centers in some B sites formerly occupied by Mn. In this way, a representative set of materials of general formula LaMn1-xCoxO3 was obtained whose composition extends from LaMnO3 to LaCoO3. These perovskites, as promising materials for oxygen reduction or oxygen evolution reactions, were characterized by several imaging (SEM), spectroscopic (XPS, EDX) and diffraction (XRD) techniques to elucidate their structure and to demonstrate the existence of composition differences between the catalytic surface and the bulk material. Specifically, it was found that lanthanum ions prevail at the surface of the catalyst but high cobalt-substitution levels stimulate the surface enrichment in B cations in their respective higher oxidation states (Mn4+ and Co3+ against Mn3+ and Co2+). This phenomenon opens the possibility of tuning their electrocatalytic properties and to synthesize suitable materials for electrochemical reactions involving molecular oxygen.