Imidazolium-modification enhances photocatalytic CO reduction on ZnSe quantum dots

Colloidal photocatalysts can utilize solar light for the conversion of CO 2 to carbon-based fuels, but controlling the product selectivity for CO 2 reduction remains challenging, in particular in aqueous solution. Here, we present an organic surface modification strategy to tune the product selectivity of colloidal ZnSe quantum dots (QDs) towards photocatalytic CO 2 reduction even in the absence of transition metal co-catalysts. Besides H 2 , imidazolium-modified ZnSe QDs evolve up to 2.4 mmol CO g ZnSe −1 (TON QD > 370) after 10 h of visible light irradiation (AM 1.5G, λ > 400 nm) in aqueous ascorbate solution with a CO-selectivity of up to 20%. This represents a four-fold increase in CO-formation yield and 13-fold increase in CO-selectivity compared to non-functionalized ZnSe QDs. The binding of the thiolated imidazolium ligand to the QD surface is characterized quantitatively using 1 H-NMR spectroscopy and isothermal titration calorimetry, revealing that a subset of 12 to 17 ligands interacts strongly with the QDs. Transient absorption spectroscopy reveals an influence of the ligand on the intrinsic charge carrier dynamics through passivating Zn surface sites. Density functional theory calculations indicate that the imidazolium capping ligand plays a key role in stabilizing the surface-bound *CO 2 − intermediate, increasing the yield and selectivity toward CO production. Overall, this work unveils a powerful tool of using organic capping ligands to modify the chemical environment on colloids, thus enabling control over the product selectivity within photocatalyzed CO 2 reduction. A photocatalyst system consisting of ZnSe quantum dots modified with a thiolated imidazolium capping ligand for visible light-driven reduction of aqueous CO 2 to CO is reported without the need for a metal complex co-catalyst.