Covalent Organic Frameworks Containing Dual O2 Reduction Centers for Overall Photosynthetic Hydrogen Peroxide Production

Abstract Covalent organic frameworks (COFs) are highly desirable for achieving high‐efficiency overall photosynthesis of hydrogen peroxide (H 2 O 2 ) via molecular design. However, precise construction of COFs toward overall photosynthetic H 2 O 2 remains a great challenge. Herein, we report the crystalline s ‐heptazine‐based COFs (HEP‐TAPT‐COF and HEP‐TAPB‐COF) with separated redox centers for efficient H 2 O 2 production from O 2 and pure water. The spatially and orderly separated active sites in HEP‐COFs can efficiently promote charge separation and enhance photocatalytic H 2 O 2 production. Compared with HEP‐TAPB‐COF, HEP‐TAPT‐COF exhibits higher H 2 O 2 production efficiency for integrating dual O 2 reduction active centers of s ‐heptazine and triazine moieties. Accordingly, HEP‐TAPT‐COF bearing dual O 2 reduction centers exhibits a remarkable solar‐to‐chemical energy efficiency of 0.65 % with a high apparent quantum efficiency of 15.35 % at 420 nm, surpassing previously reported COF‐based photocatalysts.