Ultrahigh Photocatalytic CO₂ Reduction Efficiency and Selectivity Manipulation by Single‐Tungsten‐Atom Oxide at the Atomic Step of TiO₂

The photocatalytic CO₂ reduction reaction is a sustainable route to the direct conversion of greenhouse gases into chemicals without additional energy consumption. Given the vast amount of greenhouse gas, numerous efforts have been devoted to developing inorganic photocatalysts, e.g., titanium dioxide (TiO₂ ), due to their stability, low cost, and environmentally friendly properties. However, a more efficient TiO₂ photocatalyst without noble metals is highly desirable for CO₂ reduction, and it is both difficult and urgent to produce selectively valuable compounds. Here, a novel "single-atom site at the atomic step" strategy is developed by anchoring a single tungsten (W) atom site with oxygen-coordination at the intrinsic steps of classic TiO₂ nanoparticles. The composition of active sites for CO₂ reduction can be controlled by tuning the additional W⁵⁺ to form W⁵⁺ -O-Ti³⁺ sites, resulting in both significant CO₂ reduction efficiency with 60.6 μmol g^- ¹ h^- ¹ and selectivity for methane (CH₄ ) over carbon monoxide (CO), which exceeds those of pristine TiO₂ by more than one order of magnitude. The mechanism relies on the accurate control of the single-atom sites at step with 22.8% coverage of surface sites and the subsequent excellent electron-hole separation along with the favorable adsorption-desorption of intermediates at the sites.