Reductive Carbon–Carbon Coupling on Metal Sites Regulates Photocatalytic CO ₂ Reduction in Water Using ZnSe Quantum Dots

Colloidal quantum dots (QDs) consisting of precious‐metal‐free elements show attractive potentials towards solar‐driven CO 2 reduction. However, the inhibition of hydrogen (H 2 ) production in aqueous solution remains a challenge. Here, we describe the first example of a carbon–carbon (C−C) coupling reaction to block the competing H 2 evolution in photocatalytic CO 2 reduction in water. In a specific system taking ZnSe QDs as photocatalysts, the introduction of furfural can significantly suppress H 2 evolution leading to CO evolution with a rate of ≈5.3 mmol g −1 h −1 and a turnover number (TON) of >7500 under 24 h visible light. Meanwhile, furfural is upgraded to the self‐coupling product with a yield of 99.8 % based on the consumption of furfural. Mechanistic insights show that the reductive furfural coupling reaction occurs on surface Zn‐sites to consume electrons and protons originally used for H 2 production, while the CO formation pathway at surface anion vacancies from CO 2 remains.