Pyridine‐based Covalent Organic Frameworks with Pyridyl‐Imine Structures for Boosting Photocatalytic H2O2 Production via One‐Step 2e‐ Oxygen Reduction

Abstract Bipyridine‐based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H 2 O 2 ). However, the presence of imine nitrogen alters the mode of H 2 O 2 generation from an efficient one‐step two‐electron (2e − ) route to a two‐step 2e − oxygen reduction pathway. In this work, we introduce 3,3′‐bipyridine units into imine‐based COF skeletons, creating a pyridyl‐imine structure with two adjacent nitrogen atoms between the pyridine ring and imine linkage. This unique bipyridine‐like architecture can effectively suppress the two‐step 2e − ORR process at the single imine‐nitrogen site, facilitating a more efficient one‐step 2e − pathway. Consequently, the optimized pyridyl‐imine COF (PyIm‐COF) exhibits a remarkable H 2 O 2 production rate of up to 5850 μmol h −1 g −1 , nearly double that of pristine bipyridine COFs. This work provides valuable insight into the rational design of functionalized COFs for enhanced H 2 O 2 production in photocatalysis.