In situ Doping Coupling With Vacancy Regulation Induced Strong Metal‐Support Interaction in Ni/CaTiO₃ to Boost Supercharged Photothermal CO₂ Methanation

Abstract The “Solar Sabatier” reaction has emerged as a promising sustainable method for the CO₂ hydrogenation. The development of advanced metal‐support catalysts based on Strong Metal‐Support Interaction (SMSI) offers significant advantages in the activation of CO₂ and the regulation of selectivity. Herein, a novel composite Ni/CaTiO₃ catalyst consisting of Ni and Ni‐doped CaTiO₃ is synthesized and utilized in the CO₂ methanation. A noteworthy finding is that the incorporation of Ni into the CaTiO₃ matrix is instrumental in the formation of oxygen vacancies and the establishment of SMSI between Ni and CaTiO₃. The enhanced SMSI resulting from the surface‐doped Ni atoms not only facilitated effective interface contact between metallic Ni and the CaTiO₃ surface but also significantly improved the migration efficiency of hydrogen atoms reduced the reaction barrier for CO₂ methanation and optimized the rate‐limiting step, all of which are advantageous for the CO₂ methanation. Consequently, the optimized catalysts exhibited extraordinary performance, achieving a CO₂ conversion rate of 87.77%, CH₄ generation rate of 3.12 mol g_Ni⁻¹ h⁻¹, and ≈100% CH₄ selectivity under ambient pressure conditions. This investigation lays the groundwork for the design of highly active “Solar Sabatier” catalysts and offers a novel understanding of the mechanisms underlying effective SMSI.