Abstract

Platinum is the most effective electrocatalyst for the hydrogen evolution reaction in acidic solutions, but its high cost limits its wide application. Therefore, it is desirable to design catalysts that only require minimal amounts of Pt to function, but that are still highly active. Here we report hydrogen production in acidic water using a multicomponent catalyst with an ultralow Pt loading (1.4 μg per electrode area (cm2)) supported on melamine-derived graphitic tubes (GTs) that encapsulate a FeCo alloy and have Cu deposited on the inside tube walls. With a 1/80th Pt loading of a commercial 20% Pt/C catalyst, in 0.5 M H2SO4 the catalyst achieves a current density of 10 mA cm−2 at an overpotential of 18 mV, and shows a turnover frequency of 7.22 s−1 (96 times higher than that of the Pt/C catalyst) and long-term durability (10,000 cycles). We propose that a synergistic effect between the Pt clusters and single Pt atoms embedded in the GTs enhances the catalytic activity.

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Acknowledgements

This work was supported by NRF (National Honor Scientist Program: 2010-0020414) and KISTI (KSC-2016-C3-0074). We acknowledge K.-S. Lee for help with the EXAFS analysis. The EXAFS experiments were performed in the PAL beamline (6D C&S UNIST-PAL).

Author information

Affiliations

  1. Center for Superfunctional Materials, Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    • Jitendra N. Tiwari
    • , Siraj Sultan
    • , Chang Woo Myung
    • , Taeseung Yoon
    • , Nannan Li
    • , Miran Ha
    • , Ahmad M. Harzandi
    • , Dong Yeon Kim
    • , S. Selva Chandrasekaran
    • , Wang Geun Lee
    • , Varun Vij
    •  & Kwang S. Kim
  2. Department of Chemical Engineering, UNIST, Ulsan, Republic of Korea

    • Miran Ha
  3. School of Materials Science and Engineering, UNIST, Ulsan, Republic of Korea

    • Hyo Ju Park
    •  & Zonghoon Lee
  4. UNIST Central Research Facilities, UNIST, Ulsan, Republic of Korea

    • Hoju Kang
    •  & Tae Joo Shin
  5. Department of Chemistry, UNIST, Ulsan, Republic of Korea

    • Hyeon Suk Shin
    •  & Geunsik Lee

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Contributions

J.N.T. planned the experiment, electrochemical measurements and analysed the data. J.N.T. and S.S. performed physical and chemical characterizations, including the TEM analysis. S.S. and T.Y. performed the synthesis and electrochemical measurements. C.W.M., N.L., M.H., D.Y.K., S.S.C. and G.L. carried out computations. M.H., A.M.H., H.K. and T.J.S. analysed the EXAFS data. H.J.P. and Z.L. performed TEM measurements. W.G.L., V.V. and H.S.S. discussed the results. J.N.T. and K.S.K. wrote the manuscript. K.S.K. devised the connection between theory and experiment and supervised the project.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Kwang S. Kim.

Supplementary information

  1. Supplementary Information

    Supplementary Figures 1–20, Supplementary Tables 1–7, Supplementary Notes 1–2, Supplementary Discussion, Supplementary References

  2. Supplementary Video 1

    Full water splitting in acid water.

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DOI

https://doi.org/10.1038/s41560-018-0209-x