Early View e202508783
Research Article

Three-Dimensional Porphyrin and Phthalocyanine-Based Covalent Organic Frameworks for Boosting Urea Oxidation

Dr. Guanyu Qiao

Dr. Guanyu Qiao

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

Department of Radiation Oncology, China-Japan Union Hospital of Jilin University, Changchun, 130033 P.R. China

These authors contributed equally to this work.

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Dr. Bolun Wang

Dr. Bolun Wang

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

International Center of Future Science, Jilin University, Changchun, 130012 P.R. China

These authors contributed equally to this work.

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Ziyi Zhao

Ziyi Zhao

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

These authors contributed equally to this work.

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Hongde Yu

Hongde Yu

Faculty of Chemistry and Food Chemistry, TU Dresden, Dresden, 01069 Germany

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Jingyang Lin

Jingyang Lin

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

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Yunyu Guo

Yunyu Guo

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

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Jiahuan Wang

Jiahuan Wang

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

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Dr. Lin Li

Dr. Lin Li

Electron Microscopy Center, Jilin University, Changchun, 130012 P.R. China

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Thomas Heine

Thomas Heine

Faculty of Chemistry and Food Chemistry, TU Dresden, Dresden, 01069 Germany

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Prof. Donghai Mei

Corresponding Author

Prof. Donghai Mei

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

School of Environmental Science and Engineering, Tiangong University, Tianjin, 300387 P.R. China

E-mail: [email protected]; [email protected]

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Prof. Enquan Jin

Corresponding Author

Prof. Enquan Jin

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 P.R. China

International Center of Future Science, Jilin University, Changchun, 130012 P.R. China

E-mail: [email protected]; [email protected]

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First published: 19 June 2025

Graphical Abstract

A series of three-dimensional (3D COFs) was developed with a cyt topology, facilitating the uniform dispersion and full exposure of distinct metal sites. The resulting TAPP-OFPc-COFs demonstrate exceptional electrocatalytic performance in urea oxidation. The Fe–Ni bimetallic sites synergistically ensure high efficiency and cycle stability.

Abstract

Porphyrin and phthalocyanine-based covalent organic frameworks (COFs) have emerged as versatile scaffolds for developing high-performance photo- and electrocatalysts. By enabling precise anchoring of metal species onto their cores, these COFs allow for meticulous tuning of chemical and electronic properties, facilitating single-atom distribution and achieving outstanding catalytic performance. However, the majority of these COFs are restricted to two-dimensional (2D) architectures, where the catalytic activity of the metal centers is often compromised due to eclipsed stacking layers, limiting their optimization potential. To address this challenge, we report the synthesis of three-dimensional (3D) porphyrin and phthalocyanine-based COFs with a cyt topology. This innovative structural arrangement facilitates the atomic-level distribution of distinct metal species across steric exposed networks, and the synergistic effect of bimetallic sites leads to exceptional electrocatalytic activity in urea oxidation reactions with a current density of 10 mA cm−2 at just 1.37 VRHE. This study not only broadens the topological diversity of 3D COFs but also establishes a platform for achieving uniform and accessible multimetal distributions, paving the way for synergistic electrocatalytic materials.

Conflict of Interests

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available in the Supporting Information of this article.

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