Engineering single‐atom equivalent trapping site for photothermal <scp>CO₂</scp> selective hydrogenation

Abstract Photothermal CO 2 hydrogenation into value‐added products represents an optimal strategy for simultaneously addressing energy and environmental crises. However, achieving high production with high selectivity for target products remains a grand challenge. Herein, we constructed an S‐scheme ZnO/CeO 2 decorated by a bifunctional Pt cocatalyst. This photothermal catalyst exhibits both remarkable yield and selectivity of the CO product. The bifunctional Pt nanoparticles can effectively enhance the separation and utilization of charge carriers, facilitating this reaction. Notably, characterization techniques, in situ experiments, and theoretical simulations have demonstrated that the generation of active surface lattice oxygen and oxygen vacancies leads to a trapping effect on carbon atoms and oxygen atoms in CO, thereby playing a crucial role in modulating CO selectivity comparable to the impact of single‐atom metals. Integrating Pt nanoparticles to promote reaction and CO‐sensitive supports for improved CO selectivity offers novel insights into designing photothermal catalysts for efficient CO 2 hydrogenation.