Singlet‐Oxygen‐Driven Cooperative Photocatalytic Coupling of Biomass Valorization and Hydrogen Peroxide Production Using Covalent Organic Frameworks

Abstract

Abstract Traditional H 2 O 2 photocatalysis primarily depends on photoexcited electrons and holes to drive oxygen reduction and water oxidation, respectively. However, singlet oxygen ( 1 O 2 ), often underappreciated, plays a pivotal role in H 2 O 2 production. Meanwhile, photocatalytic biomass conversion has attracted attention, yet studies combining H 2 O 2 synthesis with biomass valorization remain rare and typically yield low‐value products. Herein, a strategy of photocatalytic valorization of furfuryl alcohol (FFA) coupled with the efficient co‐production of H 2 O 2 is reported, enabled by covalent organic frameworks (COFs) induced, 1 O 2 ‐participated Achmatowicz rearrangement. This study introduces polyimide‐based COF‐N 0‐3 with tailored nitrogen content, representing an unprecedently efficient platform for 1 O 2 production. Remarkably, reducing the nitrogen content of the COF enhances 1 O 2 production, significantly boosting the H 2 O 2 generation rate. In FFA, the primary pathway for H 2 O 2 production is Achmatowicz rearrangement, achieving a rate ten times higher than that reliant on oxygen reduction reaction in pure water, reaching 4549 µmol g⁻¹ h⁻¹. Mechanism studies revealed 1 O 2 selectively engaged FFA, bypassing hole oxidation to trigger the Achmatowicz rearrangement, producing valuable 6‐hydroxy‐(2H)‐pyranone with 99% conversion and 92% selectivity. This work establishes a coupling strategy for simultaneous synthesis of H 2 O 2 and biochemicals, offering a transformative approach to sustainable photocatalysis.