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Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition

Nature Chemistry volume 12, pages 1035–1041 (2020)Cite this article

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Abstract

Chemical reactions that convert sp2 to sp3 hybridization have been demonstrated to be a fascinating yet challenging route to functionalize graphene. So far it has not been possible to precisely control the reaction sites nor their lateral order at the atomic/molecular scale. The application prospects have been limited for reactions that require long soaking, heating, electric pulses or probe-tip press. Here we demonstrate a spatially selective photocycloaddition reaction of a two-dimensional molecular network with defect-free basal plane of single-layer graphene. Directly visualized at the submolecular level, the cycloaddition is triggered by ultraviolet irradiation in ultrahigh vacuum, requiring no aid of the graphene Moiré pattern. The reaction involves both [2+2] and [2+4] cycloadditions, with the reaction sites aligned into a two-dimensional extended and well-ordered array, inducing a bandgap for the reacted graphene layer. This work provides a solid base for designing and engineering graphene-based optoelectronic and microelectronic devices.

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Fig. 1: Schematic illustration for the photocycloaddition of the BCM layer with graphene on Cu(111).
Fig. 2: Self-assembled BCM network on the graphene–Cu(111) substrate.
Fig. 3: Cycloaddition of the BCM network on graphene–Cu(111).
Fig. 4: Vibrations and band structure of the BCM network on graphene–Cu(111).

Data availability

The methods and materials used in this study are available in the Supplementary Information. The authors declare that all data supporting the findings of this study are available within the paper and its Supplementary Information. Correspondence and requests for materials should be addressed to M.Y, A.G., L.K or F. B.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant nos. 21473045, 51772066, 21603086, U1930402), the Engineering and Physical Sciences Research Council (grant nos. EP/L000202, EP/P020194), and the State Key Laboratory of Urban Water Resource and Environment (grant no. 2018DX04). We acknowledge X. Yang (Dalian Institute of Chemical Physics, Chinese Academy of Sciences) for the initial idea of triggering the reaction by ultraviolet irradiation and useful discussion. We also acknowledge the computational support from the Beijing Computational Science Research Center. F.R. acknowledges partial salary support from the Canada Research Chairs programme.

Author information

Author notes

  1. These authors contributed equally: Miao Yu, Chong Chen, Qi Liu.

Authors and Affiliations

  1. State Key Laboratory of Urban Water Resource and Environment, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China

    Miao Yu, Chong Chen, Guoqiang Shi, Zhuo Li & Shaoshan Wang

  2. Beijing Computational Science Research Center, Beijing, China

    Qi Liu & Pengfei Guan

  3. CEMES-CNRS, Toulouse, France

    Cristina Mattioli & André Gourdon

  4. Department of Physics, King’s College London, London, UK

    Hongqian Sang & Lev Kantorovich

  5. Institute for Interdisciplinary Research, Jianghan University, Wuhan, China

    Hongqian Sang

  6. Department of Chemistry, Xiamen University, Xiamen, China

    Wujun Huang & Mingshu Chen

  7. Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China

    Kongchao Shen, Jinping Hu & Fei Song

  8. Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin, China

    Pengcheng Ding & Ye Sun

  9. iNANO and Department of Physics and Astronomy, Aarhus University, Aarhus, Denmark

    Flemming Besenbacher

  10. INRS Centre for Energy, Materials and Telecommunications, Varennes, Canada

    Federico Rosei

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  1. Miao Yu
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Contributions

A.G., M.Y. and F.B. designed the project. C.M. and A.G. synthesized the BCM molecule. C.C., G.S., S.W. and Z.L. conducted the graphene growth/BCM–graphene reaction/STM imaging/Raman analysis. W.H., C.C. and M.C. collected the IRAS results. K.S., F.S., Z.L. and J.P. carried out the ARPES studies. Q.L., L.K., H.S., P.D. and P.G. performed the calculations. M.Y., C.C., Y.S., M.C., F.R., L.K. and F. S. analysed and interpreted the results. M.Y., C.C., L.K. and F.R. wrote the manuscript. F.B. advised the project process.

Corresponding authors

Correspondence to Miao Yu, André Gourdon, Lev Kantorovich or Flemming Besenbacher.

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Supplementary Information

Supplementary Figs. 1–15, Discussion and Tables 1–3.

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Yu, M., Chen, C., Liu, Q. et al. Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition. Nat. Chem. 12, 1035–1041 (2020). https://doi.org/10.1038/s41557-020-0540-2

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