Abstract

Hydrogen–air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal–polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering.

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References

  1. 1.

    Hydrogen to the rescue. Nat. Mater. 17, 565 (2018).

  2. 2.

    U.S. Department of Energy, Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office. Multi-Year Research, Development, and Demonstration Plan, 2011–2020. Section 3.7 Hydrogen Safety, Codes and Standards (EERE, 2015).

  3. 3.

    Wadell, C., Syrenova, S. & Langhammer, C. Plasmonic hydrogen sensing with nanostructured metal hydrides. ACS Nano 8, 11925–11940 (2014).

  4. 4.

    Wadell, C. et al. Hysteresis-free nanoplasmonic Pd–Au alloy hydrogen sensors. Nano Lett. 15, 3563–3570 (2015).

  5. 5.

    Yip, H. K. et al. Gold nanobipyramid-enhanced hydrogen sensing with plasmon red shifts reaching ≈140 nm at 2 vol% hydrogen concentration. Adv. Opt. Mater. 5, 1700740 (2017).

  6. 6.

    Liu, N., Tang, M. L., Hentschel, M., Giessen, H. & Alivisatos, A. P. Nanoantenna-enhanced gas sensing in a single tailored nanofocus. Nat. Mater. 10, 631–636 (2011).

  7. 7.

    Tittl, A. et al. Palladium-based plasmonic perfect absorber in the visible wavelength range and its application to hydrogen sensing. Nano Lett. 11, 4366–4369 (2011).

  8. 8.

    Langhammer, C., Zorić, I., Kasemo, B. & Clemens, B. M. Hydrogen storage in Pd nanodisks characterized with a novel nanoplasmonic sensing scheme. Nano Lett. 7, 3122–3127 (2007).

  9. 9.

    Sterl, F. et al. Magnesium as novel material for active plasmonics in the visible wavelength range. Nano Lett. 15, 7949–7955 (2015).

  10. 10.

    Baldi, A., Narayan, T. C., Koh, A. L. & Dionne, J. A. In situ detection of hydrogen-induced phase transitions in individual palladium nanocrystals. Nat. Mater. 13, 1143–1148 (2014).

  11. 11.

    Syrenova, S. et al. Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape. Nat. Mater. 14, 1236–1244 (2015).

  12. 12.

    Favier, F., Walter, E. C., Zach, M. P., Benter, T. & Penner, R. M. Hydrogen sensors and switches from electrodeposited palladium mesowire arrays. Science 293, 2227–2231 (2001).

  13. 13.

    Penner, R. M. A nose for hydrogen gas: fast, sensitive H2 sensors using electrodeposited nanomaterials. Acc. Chem. Res. 50, 1902–1910 (2017).

  14. 14.

    Adams, B. D. & Chen, A. The role of palladium in a hydrogen economy. Mater. Today 14, 282–289 (2011).

  15. 15.

    Poyli, M. A. et al. Multiscale theoretical modeling of plasmonic sensing of hydrogen uptake in palladium nanodisks. J. Phys. Chem. Lett. 3, 2556–2561 (2012).

  16. 16.

    Schwarz, R. B. & Khachaturyan, A. G. Thermodynamics of open two-phase systems with coherent interfaces: application to metal–hydrogen systems. Acta Mater. 54, 313–323 (2006).

  17. 17.

    Hübert, T., Boon-Brett, L., Black, G. & Banach, U. Hydrogen sensors—a review. Sens. Actuat. B 157, 329–352 (2011).

  18. 18.

    Palmisano, V. et al. Selectivity and resistance to poisons of commercial hydrogen sensors. Int. J. Hydrogen Energy 40, 11740–11747 (2015).

  19. 19.

    Clerbaux, C. et al. Carbon monoxide pollution from cities and urban areas observed by the Terra/MOPITT mission. Geophys. Res. Lett. 35, L03817 (2008).

  20. 20.

    Luo, S., Wang, D. & Flanagan, T. B. Thermodynamics of hydrogen in fcc Pd−Au alloys. J. Phys. Chem. B 114, 6117–6125 (2010).

  21. 21.

    Nugroho, F. A. A., Iandolo, B., Wagner, J. B. & Langhammer, C. Bottom-up nanofabrication of supported noble metal alloy nanoparticle arrays for plasmonics. ACS Nano 10, 2871–2879 (2016).

  22. 22.

    Nugroho, F. A. A., Darmadi, I., Zhdanov, V. P. & Langhammer, C. Universal scaling and design rules of hydrogen-induced optical properties in Pd and Pd-alloy nanoparticles. ACS Nano 12, 9903–9912 (2018).

  23. 23.

    Mayer, K. M. & Hafner, J. H. Localized surface plasmon resonance sensors. Chem. Rev. 111, 3828–3857 (2011).

  24. 24.

    Fukai, Y. The Metal–Hydrogen System (Springer, 1993).

  25. 25.

    Zorić, I., Larsson, E. M., Kasemo, B. & Langhammer, C. Localized surface plasmons shed light on nanoscale metal hydrides. Adv. Mater. 22, 4628–4633 (2010).

  26. 26.

    Li, G. et al. Hydrogen storage in Pd nanocrystals covered with a metal–organic framework. Nat. Mater. 13, 802–806 (2014).

  27. 27.

    Ngene, P. et al. Polymer-induced surface modifications of Pd-based thin films leading to improved kinetics in hydrogen sensing and energy storage applications. Angew. Chem. Int. Ed. 53, 12081–12085 (2014).

  28. 28.

    Pivak, Y., Schreuders, H., Slaman, M., Griessen, R. & Dam, B. Thermodynamics, stress release and hysteresis behavior in highly adhesive Pd–H films. Int. J. Hydrogen Energy 36, 4056–4067 (2011).

  29. 29.

    Yoo, H.-W., Cho, S.-Y., Jeon, H.-J. & Jung, H.-T. Well-defined and high resolution Pt nanowire arrays for a high performance hydrogen sensor by a surface scattering phenomenon. Anal. Chem. 87, 1480–1484 (2015).

  30. 30.

    Yang, F., Kung, S.-C., Cheng, M., Hemminger, J. C. & Penner, R. M. Smaller is faster and more sensitive: the effect of wire size on the detection of hydrogen by single palladium nanowires. ACS Nano 4, 5233–5244 (2010).

  31. 31.

    Koo, W.-T. et al. Accelerating palladium nanowire H2 sensors using engineered nanofiltration. ACS Nano 11, 9276–9285 (2017).

  32. 32.

    Delmelle, R., Ngene, P., Dam, B., Bleiner, D. & Borgschulte, A. Promotion of hydrogen desorption from palladium surfaces by fluoropolymer coating. ChemCatChem 8, 1646–1650 (2016).

  33. 33.

    Nanba, Y., Tsutsumi, T., Ishimoto, T. & Koyama, M. Theoretical study of the hydrogen absorption mechanism into a palladium nanocube coated with a metal–organic framework. J. Phys. Chem. C 121, 14611–14617 (2017).

  34. 34.

    Langhammer, C., Zhdanov, V. P., Zorić, I. & Kasemo, B. Size-dependent kinetics of hydriding and dehydriding of Pd nanoparticles. Phys. Rev. Lett. 104, 135502 (2010).

  35. 35.

    Jeon, K.-J. et al. Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts. Nat. Mater. 10, 286–290 (2011).

  36. 36.

    Hong, J. et al. A highly sensitive hydrogen sensor with gas selectivity using a PMMA membrane-coated Pd nanoparticle/single-layer graphene hybrid. ACS Appl. Mater. Interfaces 7, 3554–3561 (2015).

  37. 37.

    Min, K. E. & Paul, D. R. Effect of tacticity on permeation properties of poly(methyl methacrylate). J. Polym. Sci. B 26, 1021–1033 (1988).

  38. 38.

    ISO 26142: 2010. Hydrogen Detection Apparatus – Stationary Applications (ISO, 2010).

  39. 39.

    Yamada, Y., Yamada, T., Tasaka, S. & Inagaki, N. Surface modification of poly(tetrafluoroethylene) by remote hydrogen plasma. Macromolecules 29, 4331–4339 (1996).

  40. 40.

    Fredriksson, H. et al. Hole–mask colloidal lithography. Adv. Mater. 19, 4297–4302 (2007).

  41. 41.

    Grant, A. W., Hu, Q.-H. & Kasemo, B. Transmission electron microscopy windows for nanofabricated structures. Nanotechnology 15, 1175–1181 (2004).

  42. 42.

    Slaman, M., Westerwaal, R., Schreuders, H. & Dam, B. Optical hydrogen sensors based on metal-hydrides. Proc. SPIE 8368, 836805 (2012).

  43. 43.

    Briggs, D. & Seah, M. P. Practical Surface Analysis, Auger and X-ray Photoelectron Spectroscopy (Wiley, 1990).

  44. 44.

    Nugroho, F. A. A. et al. Plasmonic nanospectroscopy for thermal analysis of organic semiconductor thin films. Anal. Chem. 89, 2575–2582 (2017).

  45. 45.

    Sauerbrey, G. Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung. Zeitschrift für Phys. 155, 206–222 (1959).

  46. 46.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

  47. 47.

    Berland, K. & Hyldgaard, P. Exchange functional that tests the robustness of the plasmon description of the van der Waals density functional. Phys. Rev. B 89, 035412 (2014).

  48. 48.

    Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

  49. 49.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

  50. 50.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

  51. 51.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

  52. 52.

    Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

  53. 53.

    Silkin, V. M., Díez Muĩo, R., Chernov, I. P., Chulkov, E. V. & Echenique, P. M. Tuning the plasmon energy of palladium-hydrogen systems by varying the hydrogen concentration. J. Phys. Condens. Matter 24, 104021 (2012).

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Acknowledgements

The authors acknowledge financial support from the Swedish Foundation for Strategic Research Framework project RMA15–0052, the Knut and Alice Wallenberg Foundation project 2016.0210 and the Polish National Science Center project 2017/25/B/ST3/00744. The authors also thank the Knut and Alice Wallenberg Foundation for their support of the infrastructure in the MC2 nanofabrication laboratory at Chalmers. The electronic structure calculations were performed on resources provided by the Swedish National Infrastructure for Computing at NSC and C3SE (projects SNIC2017–1–632, SNIC2017–12–18 and C3SE2018–1–6). The authors thank J. Fritzsche for help with the SEM figure and M. Slaman (VU Amsterdam) for FTIR measurements.

Author information

Affiliations

  1. Department of Physics, Chalmers University of Technology, Göteborg, Sweden

    • Ferry A. A. Nugroho
    • , Iwan Darmadi
    • , Lucy Cusinato
    • , Arturo Susarrey-Arce
    • , Tomasz J. Antosiewicz
    • , Anders Hellman
    • , Vladimir P. Zhdanov
    •  & Christoph Langhammer
  2. Department of Chemical Engineering, Delft University of Technology, Delft, the Netherlands

    • Herman Schreuders
    • , Lars J. Bannenberg
    •  & Bernard Dam
  3. Center for Electron Nanoscopy, Technical University of Denmark, Kongens Lyngby, Denmark

    • Alice Bastos da Silva Fanta
    • , Shima Kadkhodazadeh
    •  & Jakob B. Wagner
  4. Faculty of Physics, University of Warsaw, Warsaw, Poland

    • Tomasz J. Antosiewicz
  5. Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk, Russia

    • Vladimir P. Zhdanov

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Contributions

F.A.A.N. and C.L. designed the experiments, analysed the data and wrote the manuscript. F.A.A.N. and I.D. fabricated the sensors. F.A.A.N. performed sensing measurements on PTFE sensors. F.A.A.N. and I.D. performed sensing measurements on PMMA and tandem sensors. L.C. and A.H. executed the DFT calculations. A.S.-A. performed the XPS analysis. H.S. deposited the PTFE thin films. L.J.B. and B.D. performed the XRD analysis. A.B.d.S.F. and J.B.W. performed the TKD analysis. S.K. performed the STEM-EDS analysis. T.J.A. performed the FDTD simulations. V.P.Z. contributed the theoretical analysis on the sensor kinetics and PTFE strain. B.D. and C.L. coined the initial idea. C.L. coordinated the project.

Competing interests

C.L. is co-founder of a spin-off company that markets nanoplasmonic sensor-based technologies. The rest of the authors declare no competing interests.

Corresponding authors

Correspondence to Ferry A. A. Nugroho or Christoph Langhammer.

Supplementary information

  1. Supplementary Information

    Supplementary Sections 1–14, Supplementary Tables 1–4, Supplementary Figures 1–49, Supplementary References 1–87

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https://doi.org/10.1038/s41563-019-0325-4