Ru-promoted perovskites as effective redox catalysts for CO2 splitting and methane partial oxidation in a cyclic redox scheme

Abstract

The current study reports A_xA′_1−xB_yB′_1−yO_3−δ perovskite redox catalysts (RCs) for CO₂-splitting and methane partial oxidation (POx) in a cyclic redox scheme. Strontium (Sr) and iron (Fe) were chosen as A and B site elements with A′ being lanthanum (La), samarium (Sm) or yttrium (Y), and B′ being manganese (Mn) or titanium (Ti) to tailor their equilibrium oxygen partial pressures (P_O2s) for CO₂-splitting and methane partial oxidation. DFT calculations were performed for predictive optimization of the oxide materials whereas experimental investigation confirmed the DFT-predicted redox performance. The redox kinetics of the RCs improved significantly by 1 wt% ruthenium (Ru) impregnation without affecting their redox thermodynamics. Ru-impregnated LaFe_0.375Mn_0.625O₃ (A = 0, A′ = La, B = Fe, and B′ = Mn) was the most promising RC in terms of its superior redox performance (CH₄/CO₂ conversion >90% and CO selectivity ∼95%) at 800 °C. Long-term redox testing over Ru-impregnated LaFe_0.375Mn_0.625O₃ indicated a stable performance during the first 30 cycles followed by an ∼25% decrease in the activity during the last 70 cycles. Air treatment was effective to reactivate the redox catalyst. Detailed characterizations revealed the underlying mechanism of the redox catalyst deactivation and reactivation. This study not only validated a DFT-guided mixed oxide design strategy for CO₂ utilization but also provides potentially effective approaches to enhance redox kinetics and long-term redox catalyst performance.