Production of H ₂ O ₂ via Energy Transfer Photocatalysis by Coupling with Furfuryl Alcohol Conversion over an Amide‐Functionalized Heptazine Framework

Abstract

Abstract Photocatalytic oxygen reduction provides a sustainable approach for hydrogen peroxide (H 2 O 2 ) synthesis, but the charge carrier‐based pathway is severely limited by inefficient charge separation and redox decomposition of the produced H 2 O 2 . Energy transfer photocatalysis (EnTP) is an alternative charge‐carrier‐free route for H 2 O 2 synthesis. Herein, we propose a strategy of killing two birds with one stone to simultaneously realize the synthesis of H 2 O 2 and conversion of a biomass derivative by coupling EnTP with the Achmatowicz reaction. Results show efficient production of H 2 O 2 at a rate of 14.6 mmol g cat −1  h −1  and an apparent quantum yield (AQY) of 44.1% at 420 nm, coupled with the conversion of biomass‐derived furfuryl alcohol (FFA) into hydroxy‐2H‐pyran‐3(6H)‐one with a high selectivity of 85.9%. Such a performance was attributed to the efficient EnTP over the amide‐functionalized heptazine framework photocatalyst for singlet oxygen generation, which induces the FFA conversion and concurrently produces H 2 O 2 . A systematic study of the photoexcitation process of the catalysts reveals that the amide functionalization significantly improves the intersystem crossing (ISC) efficiency, as the structural modification optimizes the electronic structure and thus tunes the composition and distribution of energy bands.