Intercalated cobaltporphyrin-based cofs materials, methods of synthesis thereof, and applications thereof for electrocatalytic oxygen reduction

By inserting molecular struts between the layers of COFs materials, the interlayer space is opened up, and a vertically extended covalent organic framework is constructed, which solves the problem of the limitation of π-π interaction between the layers of traditional COFs materials and achieves highly efficient electrocatalytic oxygen reduction performance.

CN122255387APending Publication Date: 2026-06-23SHAANXI NORMAL UNIV
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
SHAANXI NORMAL UNIV
Filing Date
2026-04-01
Publication Date
2026-06-23

AI Technical Summary

Technical Problem

Traditional COFs materials form π-π interactions between layers, resulting in layered or folded frameworks that restrict guest molecules from entering the xy space, hindering structural development and functional exploration. In particular, there is a lack of intercalation research when metal carboxylic molecules are used as monomers to construct COFs materials.

Method used

By inserting molecular struts as spacers between two-dimensional layers and utilizing coordination bonds to replace the π-π interactions between layers, the interlayer space is opened up, and vertically extended covalent organic framework (COF) materials are constructed, providing new channels and active sites.

Benefits of technology

The monomer types of COFs materials were expanded, and the electrocatalytic performance of the materials was significantly improved. In particular, the intercalated cobalt carboxylic acid COFs materials showed excellent catalytic activity, selectivity and stability in the electrocatalytic oxygen reduction reaction, with a half-wave potential of 0.94 V (vs. RHE), an electron transfer number of close to 3.84, and a current retention rate of 97% after 10 h stability test.

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Abstract

The application discloses an intercalated cobaltporphyrin-based COFs material, a synthesis method thereof and application of the material in electrocatalytic oxygen reduction, and the material is prepared by subjecting 5,10,15-tri (4-aldehyde phenyl) cobalt (III) porphyrin with an axial ligand pyrazine or bipyridine to a Shiff-Base reaction with p-phenylenediamine, thereby forming a COFs structure extending along a z-axis direction. The axial ligand is inserted into an interlayer through a coordination bond, replaces traditional pi-pi interaction, effectively opens an x-y space in the interlayer, increases exposure of active sites and constructs a new guest molecule transmission channel. The COFs material has excellent chemical stability and electrocatalytic stability, a relatively high specific surface area and a clear coordination environment, and exhibits higher activity, selectivity and stability in an electrocatalytic oxygen reduction reaction, with a half-wave potential being up to 0.94 V (vs. RHE), an electron transfer number being close to 3.84 and a current retention rate being 97% after 10 hours, thereby providing a new idea for design of high-performance electrocatalytic materials.
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