Charging modulation of the pyridine nitrogen of covalent organic frameworks for promoting oxygen reduction reaction

Xiubei Yang, Qizheng An, Xuewen Li, Yubin Fu (), Shuai Yang, Minghao Liu, Qing Xu () and Gaofeng Zeng ()
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Xiubei Yang: Chinese Academy of Sciences (CAS) Shanghai
Qizheng An: University of Science and Technology of China Hefei
Xuewen Li: Chinese Academy of Sciences (CAS) Shanghai
Yubin Fu: Technische Universität Dresden Dresden
Shuai Yang: Chinese Academy of Sciences (CAS) Shanghai
Minghao Liu: Chinese Academy of Sciences (CAS) Shanghai
Qing Xu: Chinese Academy of Sciences (CAS) Shanghai
Gaofeng Zeng: Chinese Academy of Sciences (CAS) Shanghai

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract Covalent organic frameworks (COFs) are ideal templates for constructing metal-free catalysts for the oxygen reduction reaction due to their highly tuneable skeletons and controllable porous channels. However, the development of highly active sites within COFs remains challenging due to their limited electron-transfer capabilities and weak binding affinities for reaction intermediates. Herein, we constructed highly active catalytic centres by modulating the electronic states of the pyridine nitrogen atoms incorporated into the frameworks of COFs. By incorporating different pyridine units (such as pyridine, ionic pyridine, and ionic imidazole units), we tuned various properties including dipole moments, reductive ability, hydrophilicity, and binding affinities towards reaction intermediates. Notably, the ionic imidazole COF (im-PY-BPY-COF) exhibited greater activity than the neutral COF (PY-BPY-COF) and ionic pyridine COF (ion-PY-BPY-COF). Specifically, im-PY-BPY-COF demonstrated a half-wave potential of 0.80 V in 0.1 M KOH, outperforming other metal-free COFs. Theoretical calculations and in situ synchrotron radiation Fourier transform infrared spectroscopy confirmed that the carbon atoms in the ionic imidazole rings improved the activity by facilitating binding of the intermediate OOH* and promoting the desorption of OH*. This study provides new insights into the design of highly active metal-like COF catalysts.

Date: 2024
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DOI: 10.1038/s41467-024-46291-y

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