Abstract
In this paper, two types of conjugated, triazine-based covalent organic frameworks (COFs) with different connected linkages (imine bond and sp2-carbon-CN bond) are presented. The insignificant difference in the linkages creates a remarkable difference in their performance in visible-light-driven hydrogen generation. The fully π-conjugated two-dimensional (2D) COF with sp2-carbon-CN linkages showed an external quantum efficiency of 13.48% at 450 nm, which is an unprecedented result for COF photocatalysts. In contrast, the imine-linked 2D COF displayed almost no photoactivity. Further photoelectrochemical and quantum chemical studies provide an in-depth understanding of the catalytic mechanism. This finding provides new insight into preparing high-performance organic photocatalysts for solar energy conversion.
摘要
本文设计合成了两种具有不同连接方式(亚胺键和sp2-C–CN键)的三嗪基共价有机框架(COFs)材料. 连接单元的微小变化导致可见光驱动制氢性能的巨大差异. 具有sp2碳连接方式的全π共轭二维COFs在450 nm波长处表现出13.48%的外量子效率, 优于已报道的COFs光催化剂. 而亚胺键的二维COFs几乎没有光活性. 借助光电化学研究和量子化学计算进一步研究了二维COFs的催化机理, 为太阳能转化高性能有机光催化剂的制备提供了新的见解.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (31202117 and 51972185) and the Natural Science Foundation of Shandong Province (ZR2020ZD38).
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Liu H carried out the synthesis and photocatalysis experiment and wrote the paper; Wang D did the quantum-chemical calculations; Yu Z helped with some synthesis work; Chen Y, Li X, and Wu L contributed to the photocatalytic performance tests and general discussion of photocatalysis; Zhang R performed the fs-TA spectra of the catalyst; Chen X helped analyze the mechanism; Ding N guided the quantum-chemical calculations; Wang Y guided the synthesis; Zhao Y guided the whole research and wrote the paper.
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Experimental details and supporting data are available in the online version of the paper.
Hui Liu received his PhD degree from Qingdao University of Science and Technology in 2021. Now he is a postdoctoral researcher at Qingdao University of Science and Technology. His primary research interests focus on the preparation of highly conjugated COFs and photocatalytic applications.
Naixiu Ding obtained her PhD degree from Beihang University in 2011 and has been working at Qingdao University of Science and Technology since then. She is now a full professor at Qingdao University of Science and Technology. Her research interests focus on the structure and properties of polymer materials.
Yuancheng Wang received his PhD degree in 2018 from the Institute of Chemistry, Chinese Academy of Sciences, under the supervision of Prof. Deqing Zhang. Then, he joined Qingdao University of Science and Technology as a postdoctoral researcher and worked on the construction and applications of novel COFs under the supervision of Prof. Zhibo Li and Prof. Yingjie Zhao. In 2021, he joined the College of Polymer Science and Engineering, Qingdao University of Science and Technology. His current research focuses on the development of highly conjugated COFs and their potential applications in photocatalysis.
Yingjie Zhao obtained his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences, in 2011. From 2011 to 2016, he did post-doctoral research at the University of Geneva and ETH Zürich. In 2016, he went back to China and joined Qingdao University of Science and Technology. Currently, he is a full professor at Qingdao University of Science and Technology. The research interests of Zhao’s group focus on the design and synthesis of crystalline, highly conjugated 2D and 3D polymers and their photocatalysis applications.
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Fully conjugated two-dimensional sp2-carbon covalent organic frameworks for efficient photocatalytic hydrogen generation
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Liu, H., Wang, D., Yu, Z. et al. Fully conjugated two-dimensional sp2-carbon covalent organic frameworks for efficient photocatalytic hydrogen generation. Sci. China Mater. 66, 2283–2289 (2023). https://doi.org/10.1007/s40843-022-2351-y
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DOI: https://doi.org/10.1007/s40843-022-2351-y