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

Weijian Wu; Zixuan Li; Shiyin Liu; Di Zhang; Bingzi Cai; Yizhao Liang; Mingxing Wu; Yaozu Liao; Xiaojia Zhao

doi:10.1002/anie.202404563

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

Angew Chem Int Ed Engl. 2024 Apr 2:e202404563. doi: 10.1002/anie.202404563. Online ahead of print.

Authors

Weijian Wu¹, Zixuan Li¹, Shiyin Liu¹, Di Zhang¹, Bingzi Cai¹, Yizhao Liang¹, Mingxing Wu¹, Yaozu Liao², Xiaojia Zhao¹

Affiliations

¹ Hebei Key Laboratory of Inorganic Nano-materials, College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang, 050024, Hebei, China.
² State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, China.

PMID: 38565431
DOI: 10.1002/anie.202404563

Abstract

Bipyridine-based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H₂O₂). However, the presence of imine nitrogen alters the mode of H₂O₂ 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 H₂O₂ 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 H₂O₂ production in photocatalysis.

Keywords: covalent organic frameworks; hydrogen peroxide; photocatalysis; pyridyl-imine structure.

Abstract

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