Affiliation:
1. Shanghai Institute of Applied Physics Chinese Academy of Science Shanghai 201210 P. R. China
2. University of Chinese Academy of Sciences Beijing 100049 P. R. China
3. CAS Key Laboratory of Low-Carbon Conversion Science and Engineering Shanghai Advanced Research Institute (SARI) Chinese Academy of Sciences (CAS) Shanghai 201210 P. R. China
4. National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei 230029 P.R. China
Abstract
AbstractMetal‐free covalent organic frameworks (COFs) have been employed to catalyze the oxygen reduction reaction (ORR). To achieve high activity and selectivity, various building blocks containing heteroatoms and groups linked by imine bonds were used to create catalytic COFs. However, the roles of linkages of COFs in ORR have not been investigated. In this work, the catalytic linkage engineering has been employed to modulate the catalytic behaviors. To create single catalytic sites while avoiding other possible catalytic sites, we synthesized COFs from benzene units linked by various bonds, such as imine, amide, azine, and oxazole bonds. Among these COFs, the oxazole‐linkage in COFs enables to catalyze the ORR with the highest activity, which achieved a half‐wave potential of 0.75 V and a limited current density of 5.5 mA cm−2. Moreover, the oxazole‐linked COF achieved a conversion frequency (TOF) value of 0.0133 S−1, which were 1.9, 1.3, and 7.4‐times that of azine‐, amide‐ and imine‐COFs, respectively. The theoretical calculation showed that the carbon atoms in oxazole linkages facilitated the formation of OOH* and promoted protonation of O* to form the OH*, thus advancing the catalytic activity. This work guides us on which linkages in COFs are suitable for ORR.
Funder
National Key Research and Development Program of China
Natural Science Foundation of Shanghai
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis
Cited by
6 articles.
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