Reactions

Pure LaFeO₃@C and LaCoO₃@C and substituted LaFe_1-xCo_xO₃ and LaCo_1-xFe_xO₃ perovskites (x = 0.10; 0.30) were used as catalysts for the liquid-phase oxidation of furfural at 150 °C and 30 bar of O₂ pressure. The perovskites were characterized by XRD, H₂-TPR, N₂ physisorption, TPR-MeOH, and XPS. The carbon in situ incorporation (@C) increases the surface area, favoring oxygen mobility leading to LaFeO₃@C stabilizing the redox pair Fe³⁺/Fe²⁺. In contrast, no evidence of the formation of a LaCoO₃@C perovskite structure through @C incorporation was observed. The gradual substitution of Fe with Co (10 and 30%) in LaFeO₃@C decreases the crystallinity, redox and basic properties, and surface area. For LaCoO₃@C, after the substitution of Co with 10 and 30% of Fe, only metal (La, Fe, Co) oxides as segregated phases were observed. The highest catalytic activity and selectivity to maleic acid of LaFeO₃@C is attributed to the higher surface area, crystalline structure, and surface-reducible Fe³⁺ species, favoring oxygen mobility and promoting their more oxidizing capacity. The lower catalytic activity of LaCoO₃@C, the Co- and Fe-substituted LaFeO₃@C and LaCoO₃@C catalysts, is attributed to the smaller surface area, and the similar selectivity towards maleic acid, 5-hydroxy-2(5H) and furanone indicates that the active site type is not modified in comparison to LaFeO₃@C.