Rational Construction of Cyanide‐Functionalized D‐A‐π‐D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water

Abstract Sacrificial‐agent‐free overall photosynthesis of H 2 O 2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O 2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide‐functionalized D−A‐π‐D system for highly efficient overall H 2 O 2 production from air and water through photocatalytic oxygen reduction reactions (ORR) and water oxidation reaction (WOR). Without using any sacrificial agent, the as‐synthesized D−A‐π‐D COF is found to enable a H 2 O 2 production rate as high as 4742 μmol h −1 g −1 from water and air and an O 2 utilization and conversion rate up to 88 %, exceeding the other D−A‐π‐A COF by respectively 1.9‐ and 1.3‐fold. Such high performance is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the unique D−A‐π‐D structure and cyanide groups. This work highlights a fundamental molecule design on advanced photocatalytic COFs with complicated D–A system for low‐cost and massive H 2 O 2 production.