Regulated High‐Spin State and Constrained Charge Behavior of Active Cobalt Sites in Covalent Organic Frameworks for Promoting Electrocatalytic Oxygen Reduction

A novel type of covalent organic frameworks has been developed by assembling definite cobalt‐nitrogen‐carbon configurations onto carbon nanotubes using linkers that have varying electronic effects. This innovative approach has resulted in an efficient electrocatalyst for oxygen reduction, which is u...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-07, Vol.62 (27), p.e202303871-n/a
Main Authors: Mei, Zhi‐yuan, Zhao, Genfu, Xia, Chenfeng, Cai, Sheng, Jing, Qi, Sheng, Xuelin, Wang, Han, Zou, Xiaoxiao, Wang, Lilian, Guo, Hong, Xia, Bao Yu
Format: Article
Language:English
Subjects:
Carbon
Carbon nanotubes
Cobalt
Configurations
Covalent Organic Framework
Electrocatalyst
Electrocatalysts
Electron transfer
Intermediates
Molecule
Nanotechnology
Nanotubes
Noble metals
Oxygen
Oxygen Reduction
Spin State
Strong interactions (field theory)
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Summary:A novel type of covalent organic frameworks has been developed by assembling definite cobalt‐nitrogen‐carbon configurations onto carbon nanotubes using linkers that have varying electronic effects. This innovative approach has resulted in an efficient electrocatalyst for oxygen reduction, which is understood by a combination of in situ spectroelectrochemistry and the bond order theorem. The strong interaction between the electron‐donating carbon nanotubes and the electron‐accepting linker mitigates the trend of charge loss at cobalt sites, while inducing the generation of high spin state. This enhances the adsorption strength and electron transfer between the cobalt center and reactants/intermediates, leading to an improved oxygen reduction capability. This work not only presents an effective strategy for developing efficient non‐noble metal electrocatalysts through reticular chemistry, but also provides valuable insights into regulating the electronic configuration and charge behavior of active sites in designing high‐performance electrocatalysts. Covalent organic frameworks (COFs) are developed by assembling definite cobalt‐nitrogen‐carbon configurations onto carbon nanotubes using linkers with different electronic effects. The resulting COFs have high‐spin state active cobalt sites, which constrain charge behaviors and serve as an efficient electrocatalyst for the oxygen reduction reaction (ORR).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202303871