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Covalent bulk functionalization of graphene

Nature Chemistry volume 3, pages 279–286 (2011)Cite this article

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Abstract

Graphene, a truly two-dimensional and fully π-conjugated honeycomb carbon network, is currently evolving into the most promising successor to silicon in micro- and nanoelectronic applications. However, its wider application is impeded by the difficulties in opening a bandgap in its gapless band-structure, as well as the lack of processability in the resultant intrinscially insoluble material. Covalent chemical modification of the π-electron system is capable of addressing both of these issues through the introduction of variable chemical decoration. Although there has been significant research activity in the field of functionalized graphene, most work to date has focused on the use of graphene oxide. In this Article, we report on the first wet chemical bulk functionalization route beginning with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Through effective reductive activation, covalent functionalization of the charged graphene is achieved by organic diazonium salts. Functionalization was observed spectroscopically, and successfully prevents reaggregation while providing solubility in common organic media.

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Figure 1: Reaction scheme.
Figure 2: Raman and AFM experiments conducted at different stages of the reduction/exfoliation/functionalization sequence with BPD.
Figure 3: Spectral fingerprints of functionalization by BPD.
Figure 4: Spatial Raman intensity analysis and statistical Raman characterization of covalently functionalized graphene sheets.
Figure 5: HRTEM micrographs of functionalized graphene derivatives.

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Acknowledgements

The authors thank the Deutsche Forschungsgemeinschaft (DFG), the Interdisciplinary Center for Molecular Materials (ICMM), the European Research Council (ERC; grant 246622 — GRAPHENOCHEM), the Graduate School Molecular Science (GSMS) and the Cluster of Excellence ‘Engineering of Advanced Materials (EAM)’ for financial support.

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Authors and Affiliations

  1. Department of Chemistry and Pharmacy and Institute of Advanced Materials and Processes (ZMP), University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany, and Dr.-Mack-Str. 81, Fürth, 90762, Germany

    Jan M. Englert, Christoph Dotzer, Frank Hauke & Andreas Hirsch

  2. Department for Material Sciences, Center of Nanoanalysis and Electron Microscopy (CENEM), University of Erlangen-Nürnberg, Cauerstrasse 6, Erlangen, 91058, Germany

    Guang Yang & Erdmann Spiecker

  3. Department of Chemistry and Pharmacy, Physical Chemistry II, University of Erlangen-Nürnberg, Egerlandstrasse 3, Erlangen, 91058, Germany

    Martin Schmid, Christian Papp, J. Michael Gottfried & Hans-Peter Steinrück

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  1. Jan M. Englert
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Contributions

F.H. and A.H. supervised the project as scientific group leader and principal investigator. J.M.E. worked out the concept, synthesized all compounds, carried out Raman, absorption, emission, IR and NMR spectroscopy, and performed AFM, SRM and optical microscopy. C.D. carried out TGA/MS characterization. E.S. and G.Y. conducted HRTEM and EDX investigations. M.S., C.P., J.M.G. and H.-P.S. carried out XPS analysis. A.H., F.H. and J.M.E. wrote the manuscript.

Corresponding author

Correspondence to Andreas Hirsch.

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The authors declare no competing financial interests.

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Englert, J., Dotzer, C., Yang, G. et al. Covalent bulk functionalization of graphene. Nature Chem 3, 279–286 (2011). https://doi.org/10.1038/nchem.1010

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