Abstract
Covalent organic framework (COF) materials have gained significant applications in electrocatalytic systems due to their structural diversity and tunable functionalities. Moreover, three-dimensional (3D) COFs exhibit multistage pore structures, exposing numerous open sites, which facilitate the oxygen reduction reaction (ORR) process. However, the advancement of 3D COFs for ORR has been hindered by challenges, including limited topologies, the scarcity of building blocks with the required reactivity and symmetries, and difficulties in determining crystalline structures. In this work, we utilized an 8-connectivity building unit and successfully constructed two isoreticular 3D COF materials, which exhibited exceptionally high catalytic activity for 2e− oxygen reduction reaction without the addition of any metal or conductive support materials, nor the pyrolyzed process. The electrochemically active surface areas (ECSAs) of the two 3D COFs were found to be 17.19 and 12.18 mF/cm2, respectively, which were significantly higher than those reported from other framework materials.
摘要
共价有机框架材料因其结构多样性和可调节的功能而在电催化系统中获得了显著的应用. 此外, 三维(3D)共价有机框架(COFs)展现出多级孔隙结构, 暴露出众多活性位点, 这有助于推进氧气还原反应(ORR)的进程. 然而, 3D COFs在ORR方面的进展受到了限制, 这些限制包括有限的拓扑结构、 缺乏具有所需反应性和对称性的构建单元, 以及确定晶体结构的困难. 在本研究中, 我们利用一种8连接性的构建单元, 成功构建了两种等网状的3D COF材料, 这些材料在无需添加任何金属或导电支撑材料, 也无需热解过程的情况下, 展现出了对2电子氧气还原反应异常高的催化活性. 两种3D COF的电化学活性表面积(ECSAs)分别为17.19和12.18 mF/cm2, 显著高于其他框架材料所报告的数据.
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Acknowledgement
This work was supported by the National Natural Science Foundation of China (22271106, 22105202, 22275185), China Postdoctoral Science Foundation (2021M693178, 2022T150650), XIREM Autonomously Deployment Project (2023GG01), Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China (2021ZZ115), Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (20230027). The authors would like to thank Shiyanjia Lab (www.shiyanjia.com) for the BET characterization.
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Author contributions Wei S and Wu X were responsible for data curation and formal analysis, while Wei S also contributedto visualization and drafting of the original manuscript, and Wu X added methodology to their collaborative efforts. They both were involved in reviewing and editing the manuscript. Zhu S and Wang Z focused on data curation and manuscript reviewing and editing. Wang J provided formal analysis and supervision, as well as visualization. Lu C-Z and Xie Y were key in securing funding, project administration, and supervision, while Lu C-Z also contributed to visualization and manuscript reviewing and editing, and Xie Y oversaw formal analysis, visualization, and extensive manuscript reviewing and editing.
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Shanyue Wei is a PhD student at the College of Materials Science & Engineering, Huaqiao University, under the guidance of Prof. Yiming Xie. His main research interests are the synthesis of 3D COF materials and their applications in energy storage.
Xiaowei Wu obtained his PhD degree in chemistry from Shanghai Jiao Tong University in 2019. He is working on his postdoctoral work in Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. His research interests focus on design and application of COF-based materials for clean and renewable energy.
Jiangli Wang received her PhD degree of radio physics from Department of Electronic Science, Xiamen University, in 2019. From 2019 to 2022, she worked in Nanchang Hangkong University. Currently, she is an engineer at Fujian Institute of Research on the structure of matter. Her research interest focuses on photoelectrocatalysis and nanometer materials.
Yiming Xie received his PhD degree from Fujian Institute of Research on the structure of matter, Chinese Academy of Sciences in 2009, under the supervision of Prof. Can-Zhong Lu. His research interests are the development of catalysts with single atoms and their applications in zinc-air batteries, applications in energy sources of polymer polymers and biomass carbon, lithium and sodium batteries, and applications of perovskite cells.
Can-Zhong Lu is a professor at the Fujian Institute of Research on the structure of matter, Chinese Academy of Sciences. Prof. Lu received his BS degree in chemistry from Xiamen University in 1986, and PhD degree from the University of Essex, England, in 1999. Prof. Lu’s research interests include organic-inorganic composite materials, and photoelectric conversion materials. He has also made some important progress in the research of organic ligands or transition metal (rare earth) small molecules connecting polyoxides to construct organic-inorganic hybrid materials and host-guest materials, transition metal luminescent materials and their devices.
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Wei, S., Wu, X., Zhu, S. et al. Efficient oxygen reduction through metal-free 3D covalent organic frameworks: a novel approach. Sci. China Mater. (2024). https://doi.org/10.1007/s40843-024-3039-8
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DOI: https://doi.org/10.1007/s40843-024-3039-8