hydrogen evolution

water splitting

photocatalytic reduction

photocatalytic production

scheme heterojunction

Angewandte Chemie

Synthesizing H 2 O 2 from water and air via a photocatalytic approach is ideal for efficient production of this chemical at small‐scale. However, the poor activity and selectivity of the 2 e − water oxidation reaction (WOR) greatly restricts the efficiency of photocatalytic H 2 O 2 production. Herein we prepare a bipyridine‐based covalent organic framework photocatalyst (denoted as COF‐TfpBpy) for H 2 O 2 production from water and air. The solar‐to‐chemical conversion (SCC) efficiency at 298 K and 333 K is 0.57 % and 1.08 %, respectively, which are higher than the current reported highest value. The resulting H 2 O 2 solution is capable of degrading pollutants. A mechanistic study revealed that the excellent photocatalytic activity of COF‐TfpBpy is due to the protonation of bipyridine monomer, which promotes the rate‐determining reaction (2 e − WOR) and then enhances Yeager‐type oxygen adsorption to accelerate 2 e − one‐step oxygen reduction. This work demonstrates, for the first time, the COF‐catalyzed photosynthesis of H 2 O 2 from water and air; and paves the way for wastewater treatment using photocatalytic H 2 O 2 solution.

Molecularly Engineered Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis