Asymmetric Bi and S Single Atoms Over Porous Single‐Crystal TiO ₂ for Efficient CO ₂ Photoreduction to Acetic Acid

Regulating multi-step photocatalytic conversion of molecules remains challenging, primarily due to the complex interplays among light absorption, reactant binding, and charge separation and transfer processes. Here, the photocatalytic conversion of CO₂ to acetic acid is effectively achieved via the triadic synergy of asymmetric Bi (Bi-O₄), S (S-O₂), and 3D porous single-crystal TiO₂, which is realized through a selective extraction process. Specifically, Bi active sites lower the energy barrier for CHO^* generation and C─C coupling; meanwhile, the S─O structure modulates Bi─O and Ti─O configurations to form strong Lewis base site ((SO_2-BiO₄)^δ-) by constructing a surface sulfate species, thereby accelerating the hydrogenation step in CO₂ reduction. The specifically designed photocatalytic system achieves a high acetic acid production rate of 66.7 µmol g^-1 h^-1 with over 89% selectivity. This design underscores the significance of engineering synergistic active sites and charge transfer to enhance photocatalytic conversion efficiency, offering valuable insight into the structure-activity relationship for developing high-performance photocatalysts.