Reductive Carbon–Carbon Coupling on Metal Sites Regulates Photocatalytic CO₂ Reduction in Water Using ZnSe Quantum Dots

Colloidal quantum dots (QDs) consisting of precious-metal-free elements show attractive potentials towards solar-driven CO₂ reduction. However, the inhibition of hydrogen (H₂ ) 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 H₂ evolution in photocatalytic CO₂ reduction in water. In a specific system taking ZnSe QDs as photocatalysts, the introduction of furfural can significantly suppress H₂ 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 H₂ production, while the CO formation pathway at surface anion vacancies from CO₂ remains.