Yue Yan, Ren Rong, He Qinggang, Wang Guangjin, Chen Hongzheng, Huang Ning
Anhui Engineering Research Centre of Carbon Neutrality, The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecular-Based Materials, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241002, China.
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
ACS Appl Mater Interfaces. 2025 Jun 18;17(24):35950-35957. doi: 10.1021/acsami.5c07160. Epub 2025 Jun 9.
Covalent organic frameworks (COFs) have been widely employed as an excellent scaffold for the electrocatalytic oxygen reduction reaction (ORR). To reach high activity and selectivity, various metal complexes have been imbedded into COFs via imine bonds to obtain ORR electrocatalysts. However, most of them suffer from passable performance and low stability due to the lack of active sites and decomposable linkage. In this work, we developed a series of dioxin-linked bimetallic COFs, which are constructed by phthalocyanine and perfluorinated phthalocyanine in checkerboard mode. The rational combination of different active metals, including Fe, Cu, Ni, and Co, as well as highly stable dioxin linkage renders these COFs as high-performance ORR electrocatalysts through a synergistic effect. Among these COFs, FePcF-CoPc-COF exhibited the highest half-wave potential of 0.87 V, which constitutes a new record value among COFs and is comparable to that of commercial Pt/C catalysts. In addition, this COF can be recycled up to 10,000 runs without significant change in half-wave potential. This work not only developed an efficient and stable ORR electrocatalyst but also developed a strategy for the construction of functional COFs for practical applications.
共价有机框架（COFs）已被广泛用作电催化氧还原反应（ORR）的优良支架。为了达到高活性和选择性，各种金属配合物已通过亚胺键嵌入到COFs中以获得ORR电催化剂。然而，由于缺乏活性位点和可分解的连接键，它们中的大多数性能一般且稳定性较低。在这项工作中，我们开发了一系列由二恶英连接的双金属COFs，它们由酞菁和全氟酞菁以棋盘模式构建而成。不同活性金属（包括Fe、Cu、Ni和Co）的合理组合，以及高度稳定的二恶英连接键，通过协同效应使这些COFs成为高性能的ORR电催化剂。在这些COFs中，FePcF-CoPc-COF表现出最高的半波电位0.87 V，这在COFs中构成了一个新的记录值，并且与商业Pt/C催化剂相当。此外，这种COF可以循环使用多达10000次，半波电位没有明显变化。这项工作不仅开发了一种高效稳定的ORR电催化剂，还为构建用于实际应用的功能性COFs制定了一种策略。
