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Enhancing the photoelectrocatalytic performance of metal-free graphdiyne-based catalyst

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Abstract

As a new member of the carbon family, graphdiyne is an intrinsic semiconductor featuring a natural bandgap, which endues it potential for direct application in photoelectric devices. However, without cooperating with other active materials, conventional hexacetylene-benzene graphdiyne (HEB-GDY) shows poor performances in photocatalysis and photoelectric devices due to its non-ideal visible light absorption, low separation efficiency of the photogenerated carriers and insufficient sites for hydrogen production. Herein, we report a molecular engineering strategy for the regulation of GDY-based carbon materials, by incorporating a strong pyrene absorption group into the matrix of graphdiyne, to obtain pyrenyl graphdiyne (Pyr-GDY) nanofibers through a modified Glaser-Hay coupling reaction of 1,3,6,8-tetraethynylpyrene (TEP) monomers. For comparison, phenyl graphdiyne (Phe-GDY) nanosheets were also constructed using 1,3,4,6-tetraethynylbenzene (TEB) as a monomer. Compared with Phe-GDY, Pyr-GDY exhibits a wider visible light absorption band, promoted efficiency of the charge separation/transport and more sufficient active sites for water reduction. As a result, Pyr-GDY alone displays superior photoelectrocatalytic performance for water splitting, giving a cathode photocurrent density of ~138 μA cm−2 at a potential of −0.1 Vversus normal hydrogen electrode (NHE) in neutral aqueous solution, which is almost ten and twelve times as high as those of Phe-GDY (14 μA cm−2) and HEB-GDY (12 μA cm−2), respectively. Such a performance is also superior to those of most reported carbon-based metal-free photocathode. The results of theoretical calculations reveal that the carbon atoms in the acetylene bonds are the active sites for proton reduction. This work offers a new strategy for the construction of graphdiyne-based metal-free photo-electrocatalysts with enhanced photoelectrocatalytic performance.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2017YFA0700104), the National Natural Science Foundation of China (21790052, 21702146, 21805207) and 111 Project of China (D17003).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. International Joint Laboratory of Materials Microstructure, Ministry of Education, Institute for New Energy Materials and Low Carbon Technologies, School of Material Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China

    Ming Li, Hong-Juan Wang, Chao Zhang, Yong-Bin Chang, Sheng-Jie Li, Wen Zhang & Tong-Bu Lu

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  1. Ming Li
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  2. Hong-Juan Wang
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  3. Chao Zhang
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Correspondence to Wen Zhang or Tong-Bu Lu.

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Li, M., Wang, HJ., Zhang, C. et al. Enhancing the photoelectrocatalytic performance of metal-free graphdiyne-based catalyst. Sci. China Chem. 63, 1040–1045 (2020). https://doi.org/10.1007/s11426-020-9763-9

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