Xu Xiaoyi, Feng Yaoqian, Chen Hongzheng, Huang Ning
State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, China.
J Am Chem Soc. 2025 May 14;147(19):16653-16660. doi: 10.1021/jacs.5c04944. Epub 2025 Apr 30.
The construction of semiconducting covalent organic frameworks (COFs) via single-component self-polymerization is of broad interest in reticular chemistry. Herein, two semiconducting polyaromatic COFs with all-fused-ring conjugation structures were synthesized through the self-aldol condensation of indanone-based building blocks. The resulting COFs exhibit -type semiconducting properties and exceptional stability under harsh acidic and alkaline conditions. The electrical conductivity and charge carrier mobility of the polyaromatic COFs reached up to 5.5 × 10 S cm and 0.62 cm V s, which ranked as the highest values among -type semiconducting COFs. The high crystallinity, intrinsic porosity, excellent conductivity, and abundant five-membered rings as active sites render these COFs as effective metal-free electrocatalysts toward oxygen reduction reaction (ORR). Notably, one of these COFs shows a half-wave potential of up to 0.77 V under alkaline conditions, which constitutes one of the highest values among the reported metal-free ORR electrocatalysts. In addition, owing to the strong robustness of the polyaromatic COFs, they also exhibit long-term catalytic durability. This study not only expands the diversity of semiconducting COFs but also establishes new paradigms for the development of high-performance metal-free electrocatalysts toward the ORR process.
