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Abstract

CO₂ methanation, also known as the Sabatier reaction, is of great environmental interest as a sustainable process for energy production and storage. Herein, we report the development of a NiLa₂O₃ catalyst for CO₂ methanation prepared upon reduction of a LaNiO₃ perovskite precursor. The perovskite-based catalyst exhibits enhanced activity, high methane selectivity and improved stability when compared to Ni–La₂O₃ prepared through conventional impregnation methods. The transformation of the LaNiO₃ perovskite precursor upon thermal activation in H₂ was found to have a profound impact on the catalytic properties of the resulting material. The size and stability of exsolved Ni nanoparticles after prolonged reaction were investigated using ex situ electron microscopy. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy, as well as soft and tender X-ray photoelectron spectroscopies (AP-XPS/HAXPES), provides detailed insights into the evolution of bulk and surface phases during the transition of the perovskite to its active catalytic state. Our findings indicate that processes beyond the well-established exsolution of nanoparticles, such as lanthana spillover onto nickel, may occur during H₂ activation. More importantly, in situ spectroscopy under CO₂ methanation conditions revealed that the surface's affinity for La-hydroxide or La-carbonate formation significantly influences the reactivity. Specifically, we found that La-hydroxide acts as a precursor for the formation of La-oxycarbonate (hexagonal La₂O₂CO₃ phase), a crucial element of the active exsolved catalyst. In contrast, in the absence of La-hydroxide, La-carbonates (La₂(CO₃)₃) formed on the surface, blocking the active sites of the supported catalyst. Our research examines hitherto unrecognized processes affecting the reactivity of exsolved perovskites, highlighting LaNiO₃ as a promising catalyst for CO₂ methanation.