Well-defined Co9S8 cages enable the separation of photoexcited charges to promote visible-light CO2 reduction

Abstract

Exploring affordable cocatalysts with high performance for boosting charge separation and CO₂ activation is an effective strategy to reinforce CO₂ photoreduction efficiency. Herein, well-defined Co₉S₈ cages are exploited as a nonprecious promoter for visible-light CO₂ reduction. The Co₉S₈ cages are prepared via a multistep strategy with ZIF-67 particles as the precursor and fully characterized by physicochemical techniques. The hollow Co₉S₈ cocatalyst with a high surface area and profuse catalytically active centers is discovered to accelerate separation and transfer of light-induced charges, and strengthen concentration and activation of CO₂ molecules. In a hybrid photosensitized system, these Co₉S₈ cages efficiently promote the deoxygenative reduction of CO₂ to generate CO, with a high yield rate of 35 μmol h⁻¹ (i.e., 35 mmol h⁻¹ g⁻¹). Besides, this cocatalyst is also of high stability for the CO₂ photoreduction reaction. Density functional theory (DFT) calculations reveal that the Ru(bpy)₃²⁺ photosensitizer is strongly absorbed on the Co₉S₈ (311) surface through forming four Co–C bonds, which can serve as the “bridges” to ensure quick electron transfer from the excited photosensitiser to the active Co₉S₈ cocatalyst, thus promoting the separation of photoexcited charges for ehannced CO₂ reduction performance.