Surface‐Integrating Oxygen Vacancy and Cu_xO Nanodots Enabling Synergistic Electric Field and Dual Catalytic Sites Boosting CO₂ Photoreduction

Abstract High carrier separation efficiency and rapid surface catalytic reaction are crucial for enhancing catalytic CO₂ photoreduction reaction. Herein, integrated surface decoration strategy with oxygen vacancies (Ov) and anchoring Cu_xO (1 < x < 2) nanodots below 10 nm is realized on Bi₂MoO₆ for promoting CO₂ photoreduction performance. The charge interaction between Ov and anchored Cu_xO enables the formation of enhanced internal electric field, which provides a strong driving force for accelerating the separation of photocharge carriers on the surface of Bi₂MoO₆ (η_surf ≈71%). They can also cooperatively reduce the surface work function of Bi₂MoO₆, facilitating the migration of carrier to the surface. Meanwhile, surface‐integrated Ov and Cu_xO nanodots allowing dual catalytic sites strengthens the adsorption and activation CO₂ into *CO₂ over Bi₂MoO₆, considerably boosting the progression of CO₂ conversion process. In the absence of co‐catalyst or sacrificial agent, Bi₂MoO₆ with Ov and Cu_xO nanodots achieves a photocatalytic CO generation rate of 12.75 µmol g⁻¹ h⁻¹, a remarkable increase of over ≈15 times that of the original counterpart. This work provides a new idea for governing charge movement behaviors and catalytic reaction thermodynamics on the basis of synergistic improvement of electric field and active sites by coupling of the internal defects and external species.