Ligand-mediated exciton dissociation and interparticle energy transfer on CsPbBr3 perovskite quantum dots for efficient CO2-to-CO photoreduction

Abstract

Perovskite quantum dots (PQDs) hold immense potential as photocatalysts for CO2 reduction due to their remarkable quantum properties, which facilitates the generation of multiple excitons, providing the necessary high-energy electrons for CO2 photoreduction. However, harnessing multi-excitons in PQDs for superior photocatalysis remains challenging, as achieving the concurrent dissociation of excitons and interparticle energy transfer proves elusive. This study introduces a ligand density-controlled strategy to enhance both exciton dissociation and interparticle energy transfer in CsPbBr3 PQDs. Optimized CsPbBr3 PQDs with the regulated ligand density exhibit efficient photocatalytic conversion of CO2 to CO, achieving a 2.26-fold improvement over unoptimized counterparts while maintaining chemical integrity. Multiple analytical techniques, including Kelvin probe force microscopy, temperature-dependent photoluminescence, femtosecond transient absorption spectroscopy, and density functional theory calculations, collectively affirm that the proper ligand termination promotes the charge separation and the interparticle transfer through ligand-mediated interfacial electron coupling and electronic interactions. This work reveals ligand density-dependent variations in the gas-solid photocatalytic CO2 reduction performance of CsPbBr3 PQDs, underscoring the importance of ligand engineering for enhancing quantum dot photocatalysis.