Metalloporphyrin-based highly conjugated three-dimensional covalent organic frameworks for the electrochemical hydrogen evolution reaction†

IF 6 2区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Materials Chemistry Frontiers Pub Date : 2024-07-20 DOI:10.1039/D4QM00499J

Dan Chen, Jia Xu, Linzonghan Liu, Qingzhu Sun, Shaoxiang Li, Qingyan Pan and Yingjie Zhao

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Abstract

Highly conjugated three-dimensional (3D) COFs are still rarely reported due to the limited availability of the π-conjugated building blocks in 3D spatial directions. In this study, we successfully constructed a 3D COF named 3D-Por-SP-COF by using orthogonal 3D spirobifluorene and a planar 2D porphyrin as π-conjugated units. The porphyrin units that existed in the unobstructed one-dimensional (1D) channel walls could efficiently chelate metal ions to form a metal-supported 3D COF (Co@3D-Por-SP-COF). This rich exposure of the metal ions as active sites can maximize the advantages of 3D COFs for the electrochemical catalytic hydrogen evolution reaction (HER). The experimental results showed that Co@3D-Por-SP-COF required small onset potentials (72 mV to reach 1.0 mA cm⁻²) and low overpotentials (175 mV to reach 10 mA cm⁻²) under alkaline conditions. Compared to many porous organic polymers, the obtained metal-based 3D COF exhibits comparable or even better electrocatalytic performance.

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用于电化学氢进化反应的金属卟啉基高共轭三维共价有机框架

由于三维空间方向上的π共轭结构单元有限，高度共轭的三维 COF 仍鲜有报道。在本研究中，我们利用正交三维螺二芴和平面二维卟啉作为π共轭单元，成功构建了一种三维 COF，命名为 3D-Por-SP-COF 。存在于畅通无阻的一维（1D）通道壁中的卟啉单元可以有效地与金属离子螯合，形成金属支持的三维（Co@3D-Por-SP-COF）。这种金属离子作为活性位点的丰富暴露可以最大限度地发挥三维 COF 在电化学催化氢进化反应（HER）中的优势。实验结果表明，在碱性条件下，Co@3D-Por-SP-COF 需要较小的起始电位（72 mV，达到 1.0 mA cm -2 ）和较低的过电位（175 mV，达到 10 mA cm -2 ）。与许多多孔有机聚合物相比，所获得的金属基三维 COF 具有相当甚至更好的电催化性能。

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来源期刊

Materials Chemistry Frontiers Materials Science-Materials Chemistry

CiteScore

12.00

自引率

2.90%

发文量

313

期刊介绍： Materials Chemistry Frontiers focuses on the synthesis and chemistry of exciting new materials, and the development of improved fabrication techniques. Characterisation and fundamental studies that are of broad appeal are also welcome. This is the ideal home for studies of a significant nature that further the development of organic, inorganic, composite and nano-materials.