More Cu, more problems: Decreased CO2 conversion ability by Cu-doped La0.75Sr0.25FeO3 perovskite oxides

Abstract

The effect of Cu doping on the conversion of CO2 to CO was investigated on H2-reduced La0.75Sr0.25FeO3 perovskite oxides. Six La0.75Sr0.25Fe1−YCuYO3 perovskites, labeled Cu100*Y (with Y=0, 0.10, 0.25, 0.50, 0.75, and 1) were synthesized and characterized through X-ray diffraction (XRD), temperature-programmed oxygen vacancy formation, and temperature-programmed reduction (TPR). The incorporation of Cu facilitates the formation of oxygen vacancies at lower temperatures but also increased the instability of the perovskite. DFT simulations suggested that the Cu10 sample is favored to produce oxygen vacancies compared to Cu0 and Cu25 samples, which was consistent with experimental oxygen vacancy formation results. For the Cu0, Cu10, and Cu25 samples, temperature-programmed CO2 conversion (TPO-CO2) after isothermal H2-reduction at 450°C and post-reduction XRD were performed to evaluate the ability of the materials to convert CO2 at low temperatures and to identify the crystalline phases active in the reaction. The peak conversion of CO2 to CO was achieved 30°C lower on the Cu10 sample versus the Cu0, but less CO was produced, due to a decreased re-oxidation activity of the Cu-doped samples. CO production was inhibited in the Cu25 sample, likely due to a combined effect of poor CO2 dissociative chemisorption energies on metallic Cu and increased thermodynamic stability of the oxygen vacant perovskites. Control experiments (Cu deposited onto La0.75Sr0.25FeO3) indicated the stability of the copper-containing perovskite oxides phases was the primary limiting factor preventing CO formation from CO2.