Abstract

Graphene has recently been shown to be permeable to thermal protons1, the nuclei of hydrogen atoms, which sparked interest in its use as a proton-conducting membrane in relevant technologies1,2,3,4. However, the influence of light on proton permeation remains unknown. Here we report that proton transport through Pt-nanoparticle-decorated graphene can be enhanced strongly by illuminating it with visible light. Using electrical measurements and mass spectrometry, we find a photoresponsivity of 104 A W−1, which translates into a gain of 104 protons per photon with response times in the microsecond range. These characteristics are competitive with those of state-of-the-art photodetectors that are based on electron transport using silicon and novel two-dimensional materials5,6,7. The photo–proton effect could be important for graphene’s envisaged use in fuel cells and hydrogen isotope separation. Our observations may also be of interest for other applications such as light-induced water splitting, photocatalysis and novel photodetectors.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from $8.99

All prices are NET prices.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  1. 1.

    Hu, S. et al. Proton transport through one-atom-thick crystals. Nature 516, 227–230 (2014).

  2. 2.

    Lozada-Hidalgo, M. et al. Sieving hydrogen isotopes through two-dimensional crystals. Science 351, 68–70 (2016).

  3. 3.

    Achtyl, J. L. et al. Aqueous proton transfer across single-layer graphene. Nat. Commun. 6, 6539 (2015).

  4. 4.

    Lozada-Hidalgo, M. et al. Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping. Nat. Commun. 8, 1–5 (2017).

  5. 5.

    Koppens, F. H. et al. Photodetectors based on graphene, other two-dimensional materials and hybrid systems. Nat. Nanotech. 9, 780–793 (2014).

  6. 6.

    Lou, Z., Liang, Z. & Shen, G. Photodetectors based on two dimensional materials. J. Semicond. 37, 91001 (2016).

  7. 7.

    Yotter, R. A. & Wilson, D. M. A review of photodetectors for sensing light-emitting reporters in biological systems. IEEE Sens. J. 3, 288–303 (2003).

  8. 8.

    Miao, M., Nardelli, M. B., Wang, Q. & Liu, Y. First principles study of the permeability of graphene to hydrogen atoms. Phys. Chem. Chem. Phys. 15, 16132–16137 (2013).

  9. 9.

    Wang, W. L. & Kaxiras, E. Graphene hydrate: theoretical prediction of a new insulating form of graphene. New J. Phys. 12, 125012 (2010).

  10. 10.

    Kroes, J., Fasolino, A. & Katsnelson, M. Density functional based simulations of proton permeation of graphene and hexagonal boron nitride. Phys. Chem. Chem. Phys. 19, 5813–5817 (2017).

  11. 11.

    Feng, Y., Chen, J., Wang, E., Michelides, A. & Li, X. Hydrogenation facilitates proton transfer through two-dimensional crystals. Preprint at http://arXiv.org/abs/1704.00914 (2017).

  12. 12.

    Poltavsky, I., Zheng, L., Mortazavi, M. & Tkatchenko, A. Quantum tunneling of thermal protons through pristine graphene. Preprint at http://arXiv.org/abs/1605.06341 (2016).

  13. 13.

    Mauritz, K. & Moore, R. State of understanding of nafion. Chem. Rev. 104, 4535–4585 (2004).

  14. 14.

    Lopez-Sanchez, O., Lembke, D., Kayci, M., Radenovic, A. & Kis, A. Ultrasensitive photodetectors based on monolayer MoS2. Nat. Nanotech. 8, 497–501 (2013).

  15. 15.

    Mackowiak, V., Peupelmann, J., Ma, Y. & Gorges, A. NEP—Noise Equivalent Power (Thorlabs, accessed May 2017); https://www.thorlabs.com/images/TabImages/Noise_Equivalent_Power_White_Paper.pdf.

  16. 16.

    Oriel Product Training: Detection Systems (Oriel Instruments, retrieved May 2017); http://assets.newport.com/webDocuments-EN/images/Detection_Systems.PDF.

  17. 17.

    Bunch, J. S. et al. Impermeable atomic membranes from graphene sheets. Nano Lett. 8, 2458–2462 (2008).

  18. 18.

    Giovannetti, G. et al. Doping graphene with metal contacts. Phys. Rev. Lett. 101, 3–6 (2008).

  19. 19.

    Xu, P. et al. Self-organized platinum nanoparticles on freestanding graphene. ACS Nano 8, 2697–2703 (2014).

  20. 20.

    Chan, K. T., Neaton, J. B. & Cohen, M. L. First-principles study of metal adatom adsorption on graphene. Phys. Rev. B 77, 1–12 (2008).

  21. 21.

    Zhou, Y. et al. Enhancing the hydrogen activation reactivity of non-precious metal substrates via confined catalysis underneath graphene. Nano Lett. 16, 6058–6063 (2016).

  22. 22.

    Linic, S., Christopher, P. & Ingram, D. B. Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nat. Mater. 10, 911–921 (2011).

  23. 23.

    Brongersma, M.L., Halas, N.J. & Nordlander, P. Plasmon-induced hot carrier science and technology. Nat. Nanotech. 10, 25–34 (2015).

  24. 24.

    Graham, M. W., Shi, S.-F., Ralph, D. C., Park, J. & McEuen, P. L. Photocurrent measurements of supercollision cooling in graphene. Nat. Phys. 9, 103–108 (2012).

  25. 25.

    Gabor, M. et al. Hot carrier-assisted intrinsic photoresponse in grapahene. Science 334, 648–652 (2011).

  26. 26.

    Tielrooij, K. J. et al Generation of photovoltage in graphene on a femtosecond timescale through efficient carrier heating.Nat. Nanotech. 10, 437–443 (2015).

  27. 27.

    Sun, D. et al Ultrafast hot-carrier-dominated photocurrent in graphene.Nat. Nanotech. 7, 114–118 (2012).

  28. 28.

    Marechal, Y. The Hydrogen Bond and the Water Molecule (Elsevier, 2007).

  29. 29.

    Konstantatos, G. et al. Hybrid graphene–quantum dot phototransistors with ultrahigh gain. Nat. Nanotech. 7, 363–368 (2012).

  30. 30.

    McFarlane, S. L., Day, B. A., McEleney, K., Freund, M. S. & Lewis, N. S. Designing electronic/ionic conducting membranes for artificial photosynthesis. Energy Environ. Sci. 4, 1700–1703 (2011).

Download references

Acknowledgements

The authors acknowledge support from the Lloyd’s Register Foundation, EPSRC (EP/N010345/1), the European Research Council ARTIMATTER project (ERC-2012-ADG) and from Graphene Flagship. M.L.-H. acknowledges a Leverhulme Early Career Fellowship.

Author information

Affiliations

  1. School of Physics & Astronomy, University of Manchester, Manchester, UK

    • Marcelo Lozada-Hidalgo
    • , Sheng Zhang
    • , Vasyl G. Kravets
    • , Francisco J. Rodriguez
    • , Alexey Berdyugin
    • , Alexander Grigorenko
    •  & Andre K. Geim
  2. National Graphene Institute, University of Manchester, Manchester, UK

    • Sheng Hu

Authors

  1. Search for Marcelo Lozada-Hidalgo in:

  2. Search for Sheng Zhang in:

  3. Search for Sheng Hu in:

  4. Search for Vasyl G. Kravets in:

  5. Search for Francisco J. Rodriguez in:

  6. Search for Alexey Berdyugin in:

  7. Search for Alexander Grigorenko in:

  8. Search for Andre K. Geim in:

Contributions

A.K.G. and M.L.-H. designed and directed the project. M.L.-H. fabricated devices, performed measurements and carried out data analysis with help from S.Z. and A.B. M.L.-H. and A.K.G. wrote the manuscript. All authors contributed to discussions.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Marcelo Lozada-Hidalgo or Andre K. Geim.

Supplementary information

  1. Supplementary Information

    Supplementary Text and Supplementary Figures 1–4.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41565-017-0051-5