Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity

An Author Correction to this article was published on 05 March 2019

This article has been updated

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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Synthetic procedure and physical characterization.
Fig. 2: X-ray absorption spectra at the Pt L3 edge.
Fig. 3: Electrochemical performance and demonstration of water-splitting device.
Fig. 4: Catalytic free energies of single Pt atoms and Pt clusters/NPs on a GT surface along with the defect formation and second Pt adhesion energies.
Fig. 5: Projected density of states (PDOS) for planar tetragonal and non-planar tetrahedral defect sites of Pt.
Fig. 6: Images of single Pt atoms and Pt clusters/NPs on a GT surface.
Fig. 7: Electrochemical impedance spectroscopy.
Fig. 8: Geometry and band structures of hydrogen absorbed on Pt–N2C2/GT, Pt(111) and Pt–N2C2/GT + Pt(111).

Similar content being viewed by others

Change history

  • 05 March 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

References

  1. Zeng, K. & Zhang, D. Recent progress in alkaline water electrolysis for hydrogen production and applications. Prog. Energ. Combust. 36, 307–326 (2010).

    Google Scholar 

  2. Cabán-Acevedo, M. et al. Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide. Nat. Mater. 14, 1245–1251 (2015).

    Google Scholar 

  3. Esposito, D. V., Levin, I., Moffat, T. P. & Talin, A. A. H2 evolution at Si-based metal–insulator–semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover. Nat. Mater. 12, 562–568 (2013).

    Google Scholar 

  4. Vesborg, P. C. K., Seger, B. & Chorkendorff, I. Recent development in hydrogen evolution reaction catalysts and their practical implementation. J. Phys. Chem. Lett. 6, 951–957 (2015).

    Google Scholar 

  5. Wang, H. et al. Bifunctional non-noble metal oxide NP electrocatalysts through lithium-induced conversion for overall water splitting. Nat. Commun. 6, 7261 (2015).

    Google Scholar 

  6. Gong, M. et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nat. Commun. 5, 4695 (2014).

    Google Scholar 

  7. Yin, H. et al. Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity. Nat. Commun. 6, 6430 (2015).

    Google Scholar 

  8. Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energ. Environ. Sci. 7, 2255–2260 (2014).

    Google Scholar 

  9. Lv, H. et al. A new core/shell NiAu/Au NP catalyst with Pt-like activity for hydrogen evolution reaction. J. Am. Chem. Soc. 137, 5859–5862 (2015).

    Google Scholar 

  10. Georgakilas, V., Perman, J. A., Tucek, J. & Zboril, R. Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures. Chem. Rev. 115, 4744–4822 (2015).

    Google Scholar 

  11. Geng, X. et al. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction. Nat. Commun. 7, 10672 (2016).

    Google Scholar 

  12. Zhou, H. et al. Outstanding hydrogen evolution reaction catalyzed by porous nickel diselenide electrocatalysts. Energy Environ. Sci. 10, 1487–1492 (2017).

    Google Scholar 

  13. Wang, D. Y. et al. Highly active and stable hybrid catalyst of cobalt-doped FeS2 nanosheets–carbon nanotubes for hydrogen evolution reaction. J. Am. Chem. Soc. 137, 1587–1592 (2015).

    Google Scholar 

  14. Liu, W. et al. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide. Nat. Commun. 7, 10771 (2016).

    Google Scholar 

  15. Li, Y. H. et al. Local atomic structure modulations activate metal oxide as electrocatalysts for hydrogen evolution in acidic water. Nat. Commun. 6, 8064 (2015).

    Google Scholar 

  16. Dendooven, J. et al. Independent tuning of size and coverage of supported Pt nanoparticles using atomic layer deposition. Nat. Commun. 8, 1074 (2017).

    Google Scholar 

  17. Stephens, I. E. L. & Chorkendorff, I. Minimizing the use of platinum in hydrogen-evolving electrodes. Angew. Chem. Int. Ed. 50, 1476–1477 (2011).

    Google Scholar 

  18. Subbaraman, R. et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li+–Ni (OH)2–Pt interfaces. Science 334, 1256–1260 (2011).

    Google Scholar 

  19. Tiwari, J. N. et al. Interconnected Pt-nanodendrite/DNA/reduced-graphene-oxide hybrid showing remarkable oxygen reduction activity and stability. ACS Nano 7, 9223–9231 (2013).

    Google Scholar 

  20. Tiwari et al. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity. Nat. Commun. 4, 2221 (2013).

    Google Scholar 

  21. Sun, S. et al. Single atom catalysis using Pt/graphene achieved through atomic layer deposition. Sci. Rep. 3, 1775 (2013).

    Google Scholar 

  22. Pacios Pujadó, M. Carbon Nanotubes as Platforms for Biosensors with Electrochemical and Electronic Transduction 123–130 (Springer, Berlin/ Heidelberg, 2012).

  23. Morales-Guio, C. G., Stern, L. A. & Hu, X. L. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 43, 6555–6569 (2014).

    Google Scholar 

  24. Bockris, J. O’M. & Reddy, A. K. N. Modern Electrochemistry (Plenum, New York, 1970).

  25. Vetter, K. J. Electrochemical Kinetics (Academic, London, 1967).

  26. Voiry, D. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 12, 850–855 (2013).

    Google Scholar 

  27. Vij, V. et al. Nickel-based electrocatalysts for energy related applications: oxygen reduction, oxygen evolution, and hydrogen evolution reactions. ACS Catal. 7, 7196–7225 (2017).

    Google Scholar 

  28. Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).

    Google Scholar 

  29. Liu, Y. et al. Coupling Mo2C with nitrogen-rich nanocarbon leads to efficient hydrogen-evolution electrocatalytic sites. Angew. Chem. Int. Ed. 54, 10752–10757 (2015).

    Google Scholar 

  30. Tolman, C. A. The 16- and 18-electron rule in organometallic chemistry and homogeneous catalysis. Chem. Soc. Rev. 1, 337–353 (1972).

    Google Scholar 

  31. Lee, K. H., Oh, J., Son, J. G., Kim, H. & Lee, S.-S. Nitrogen-doped graphene nanosheets from bulk graphite using microwave irradiation. ACS Appl. Mater. Inter. 6, 6361–6368 (2014).

    Google Scholar 

  32. Lide, D. R. (ed.) CRC Handbook of Chemistry and Physics 87th edn (Taylor & Francis, Boca Raton, 2007).

  33. Madsen, G. K. H. & Singh, D. J. BoltzTraP. A code for calculating band-structure dependent quantities. Comp. Phys. Commun. 175, 67–71 (2006).

    MATH  Google Scholar 

  34. Tan, Y.-W. et al. Measurement of scattering rate and minimum conductivity in graphene. Phys. Rev. Lett. 99, 246803 (2007).

    Google Scholar 

  35. Kibsgaard, J., Jaramillo, T. F. & Besenbacher, F. Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters. Nat. Chem. 6, 248–253 (2014).

    Google Scholar 

  36. Chen, Z. et al. Core–shell MoO3–MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials. Nano Lett. 11, 4168–4175 (2011).

    Google Scholar 

  37. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    Google Scholar 

  38. 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).

    Google Scholar 

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

    Google Scholar 

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

    Google Scholar 

  41. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 78, 1396 (1997).

    Google Scholar 

  42. Tkatchenko, A. & Scheffler, M. Accurate molecular van der Waals interactions from ground-state ‘electron density and free-atom reference data. Phys. Rev. Lett. 102, 073005 (2009).

    Google Scholar 

  43. Hass, P., Tran, F., Blaha, P. & Schwarz, K. Construction of an optimal GGA functional for molecules and solids. Phys. Rev. B 83, 205117 (2011).

    Google Scholar 

  44. Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413 (1999).

    Google Scholar 

  45. Wellendorff, J. & Thomas, B. On the importance of gradient-corrected correlation for van der Waals density functionals. Top. Catal. 54, 1143–1150 (2011).

    Google Scholar 

  46. Baumer, M. & Freund, H.-J. J Metal deposits on well-ordered oxide films. Prog. Surf. Sci. 61, 127–198 (1999).

    Google Scholar 

  47. Koningsberger, D. C. & Prints, R. X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES (Wiley, New York, 1988).

  48. Stöhr, J. NEXAFS Spectroscopy (Springer, 1992).

  49. Duchesne, P. N., Chen, G., Zheng, N. & Zhang, P. Local structure, electronic behavior, and electrocatalytic reactivity of CO-reduced platinum-iron oxide NPs. J. Phys. Chem. C 117, 26324–26333 (2013).

    Google Scholar 

  50. Boita, J. et al. Reversible sulfidation of Pt0.3Pd0.7 NPs investigated by in situ time-resolved XAS. J. Phys. Chem. C 118, 5538–5544 (2014).

    Google Scholar 

Download references

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

Authors and Affiliations

Authors

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.

Corresponding author

Correspondence to Kwang S. Kim.

Ethics declarations

Competing interests

The authors declare no competing 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 Figures 1–20, Supplementary Tables 1–7, Supplementary Notes 1–2, Supplementary Discussion, Supplementary References

Supplementary Video 1

Full water splitting in acid water.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tiwari, J.N., Sultan, S., Myung, C.W. et al. Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity. Nat Energy 3, 773–782 (2018). https://doi.org/10.1038/s41560-018-0209-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

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

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing