Ketones as Molecular Co‐catalysts for Boosting Exciton‐Based Photocatalytic Molecular Oxygen Activation

Excitonic processes in semiconductors open up the possibility for pursuing photocatalytic organic synthesis. However, the insufficient spin relaxation and robust nonradiative decays in semiconductors place restrictions on both quantum yield and selectivity of these reactions. Herein, by taking polymeric carbon nitride (PCN)/acetone as a prototypical system, we propose that extrinsic aliphatic ketones can serve as molecular co-catalysts for promoting spin-flip transition and suppressing non-radiative energy losses. Spectroscopic investigations indicate that hot excitons in PCN can be transferred to ketones, while triplet excitons in ketones can be transferred to PCN. As such, the PCN/ketone systems exhibit considerable triplet-exciton accumulation and extended visible-light response, leading to excellent performance in exciton-based photocatalysis, such as singlet oxygen generation. This work provides a fundamental understanding of energy harvesting in semiconductor/molecule systems, and paves the way for optimizing exciton-based photocatalysis via molecular co-catalyst design.