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 CO 2 hydrogenation. The development of advanced metal‐support catalysts based on Strong Metal‐Support Interaction (SMSI) offers significant advantages in the activation of CO 2 and the regulation of selectivity. Herein, a novel composite Ni/CaTiO 3 catalyst consisting of Ni and Ni‐doped CaTiO 3 is synthesized and utilized in the CO 2 methanation. A noteworthy finding is that the incorporation of Ni into the CaTiO 3 matrix is instrumental in the formation of oxygen vacancies and the establishment of SMSI between Ni and CaTiO 3 . The enhanced SMSI resulting from the surface‐doped Ni atoms not only facilitated effective interface contact between metallic Ni and the CaTiO 3 surface but also significantly improved the migration efficiency of hydrogen atoms reduced the reaction barrier for CO 2 methanation and optimized the rate‐limiting step, all of which are advantageous for the CO 2 methanation. Consequently, the optimized catalysts exhibited extraordinary performance, achieving a CO 2 conversion rate of 87.77%, CH 4 generation rate of 3.12 mol g Ni −1 h −1 , and ≈100% CH 4 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.