Ti‐doped CeO2 Stabilized Single‐Atom Rhodium Catalyst for Selective and Stable CO2 Hydrogenation to Ethanol

Abstract Development of effective and stable catalysts for CO 2 hydrogenation into ethanol remains a challenge. Herein, we report that Rh 1 /CeTiO x single‐atom catalyst constructed by embedding monoatomic Rh onto Ti‐doped CeO 2 support has shown a super high ethanol selectivity (≈99.1 %), record‐breaking turnover frequency (493.1 h −1 ), and outstanding stability. Synergistic effects of Ti‐doption and monoatomic Rh contribute to this excellent catalytic performance by firstly facilitating oxygen vacancies formation to generate oxygen‐vacancy‐Rh Lewis‐acid‐base pairs, which favor CO 2 adsorption and activation, cleavage of C−O bonds in CH x OH* and COOH* into CH x * and CO* species, subsequent C−C coupling and hydrogenation into ethanol, and secondly generating strong Rh−O bond by Ti‐doping‐induced crystal reconstruction, which contributes to striking stability. This work highlights the importance of support elaborating regulation for single‐atom catalyst design to substantially improve the catalytic performance.