One‐Dimensional Covalent Organic Frameworks for the 2e− Oxygen Reduction Reaction

• Published in: Angewandte Chemie International Edition Vol. 62; no. 14; pp. e202218742 - n/a
• Main Authors: An, Shuhao, Li, Xuewen, Shang, Shuaishuai, Xu, Ting, Yang, Shuai, Cui, Cheng‐Xing, Peng, Changjun, Liu, Honglai, Xu, Qing, Jiang, Zheng, Hu, Jun
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 27.03.2023
• Edition: International ed. in English
• Subjects: Active sites; Catalysis; Chemical reduction; Covalent Organic Frameworks; Edge Sites; Electrolytes; Hydrogen peroxide; Metal-Free Catalysts; One Dimensional Topology; Oxygen Reduction Reaction; Oxygen reduction reactions; Selectivity; Surface area; Surface stability; Metal-Free Catalysts; Oxygen Reduction Reaction; Edge Sites; One Dimensional Topology; Covalent Organic Frameworks
• DOI: 10.1002/anie.202218742
• ISSN: 1433-7851; 1521-3773

Two‐dimensional covalent organic frameworks (2D COFs) are often employed for electrocatalytic systems because of their structural diversity. However, the efficiency of atom utilization is still in need of improvement, because the catalytic centers are located in the basal layers and it is difficult for the electrolytes to access them. Herein, we demonstrate the use of 1D COFs for the 2e− oxygen reduction reaction (ORR). The use of different four‐connectivity blocks resulted in the prepared 1D COFs displaying good crystallinity, high surface areas, and excellent chemical stability. The more exposed catalytic sites resulted in the 1D COFs showing large electrochemically active surface areas, 4.8‐fold of that of a control 2D COF, and thus enabled catalysis of the ORR with a higher H2O2 selectivity of 85.8 % and activity, with a TOF value of 0.051 s−1 at 0.2 V, than a 2D COF (72.9 % and 0.032 s−1). This work paves the way for the development of COFs with low dimensions for electrocatalysis. Electrocatalysis of the oxygen reduction reaction by a 2e− pathway has been achieved using two one‐dimensional covalent organic frameworks (COFs). The imine linkages led to higher activity and selectivity than two‐dimensional COFs, without the need to introduce other heteroatoms.