Giant photoeffect in proton transport through graphene membranes

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 options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Influence of illumination on proton transport through graphene activated with Pt nanoparticles.
Fig. 2: Photo–proton effect observed by mass spectrometry and microsecond time response.

References

  1. 1.

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

    Article  Google Scholar 

  2. 2.

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

    Article  Google Scholar 

  3. 3.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  5. 5.

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

    Article  Google Scholar 

  6. 6.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  9. 9.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  18. 18.

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

    Google Scholar 

  19. 19.

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

    Article  Google Scholar 

  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).

    Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  23. 23.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  25. 25.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  27. 27.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

Authors

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.

Corresponding authors

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

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Text and Supplementary Figures 1–4.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Lozada-Hidalgo, M., Zhang, S., Hu, S. et al. Giant photoeffect in proton transport through graphene membranes. Nature Nanotech 13, 300–303 (2018). https://doi.org/10.1038/s41565-017-0051-5

Download citation

Further reading

Search

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research