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:

Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules

Nature Energy volume 4, pages 107–114 (2019)Cite this article

Subjects

Abstract

High-performance hydrogen evolution reaction (HER) catalysts are compelling for the conversion of renewable electricity to fuels and feedstocks. The best HER catalysts rely on the use of platinum and show the highest performance in acidic media. Efficient HER catalysts based on inexpensive and Earth-abundant elements that operate in neutral (hence biocompatible) media could enable low-cost direct seawater splitting and the realization of bio-upgraded chemical fuels. In the challenging neutral-pH environment, water splitting is a multistep reaction. Here we present a HER catalyst comprising Ni and CrOx sites doped onto a Cu surface that operates efficiently in neutral media. The Ni and CrOx sites have strong binding energies for hydrogen and hydroxyl groups, respectively, which accelerates water dissociation, whereas the Cu has a weak hydrogen binding energy, promoting hydride coupling. The resulting catalyst exhibits a 48 mV overpotential at a current density of 10 mA cm−2 in a pH 7 buffer electrolyte. These findings suggest design principles for inexpensive, efficient and biocompatible catalytic systems.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Catalyst design principle and HER activities of CrOx/Cu–Ni catalysts.
Fig. 2: CrOx/Cu–Ni catalyst fine structures revealed by X-ray absorption spectroscopies.
Fig. 3: Ambient pressure XPS experiments of water adsorption on CrOx/Cu–Ni.
Fig. 4: Theoretical calculation of HER activation energy on CrOx/Cu–Ni catalysts.
Fig. 5: Design and characterization of the 3D CrOx/Cu–Ni catalyst.
Fig. 6: Electrochemical characterization of CrOx/Cu–Ni on 3D Cu foam.

Similar content being viewed by others

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2014).

    Article  Google Scholar 

  2. Luo, J. et al. Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts. Science 345, 1593–1596 (2014).

    Article  Google Scholar 

  3. Zhang, B. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 352, 333–337 (2016).

    Article  Google Scholar 

  4. Zhao, S. et al. Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution. Nat. Energy 1, 16184 (2016).

    Article  Google Scholar 

  5. Zheng, Y. et al. High electrocatalytic hydrogen evolution activity of an anomalous ruthenium catalyst. J. Am. Chem. Soc. 138, 16174–16181 (2016).

    Article  Google Scholar 

  6. Strmcnik, D., Lopes, P. P., Genorio, B., Stamenkovic, V. R. & Markovic, N. M. Design principles for hydrogen evolution reaction catalyst materials. Nano Energy 29, 29–36 (2016).

    Article  Google Scholar 

  7. Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012).

    Article  Google Scholar 

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

    Article  Google Scholar 

  9. Miao, J. et al. Hierarchical Ni–Mo–S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte. Sci. Adv. 1, e1500259 (2015).

    Article  Google Scholar 

  10. Staszak-Jirkovský, J. et al. Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nat. Mater. 15, 197–203 (2016).

    Article  Google Scholar 

  11. Nichols, E. M. et al. Hybrid bioinorganic approach to solar-to-chemical conversion. Proc. Natl Acad. Sci. USA 112, 11461–11466 (2015).

    Article  Google Scholar 

  12. Liu, C., Colón, B. C., Ziesack, M., Silver, P. A. & Nocera, D. G. Water splitting–biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis. Science 352, 1210–1213 (2016).

    Article  Google Scholar 

  13. Torella, J. P. et al. Efficient solar-to-fuels production from a hybrid microbial–water-splitting catalyst system. Proc. Natl Acad. Sci. USA 112, 2337–2342 (2015).

    Article  Google Scholar 

  14. Mudiyanselage, K. et al. Importance of the metal–oxide interface in catalysis: In situ studies of the water–gas shift reaction by ambient‐pressure X‐ray photoelectron spectroscopy. Angew. Chem. Int. Ed. 52, 5101–5105 (2013).

    Article  Google Scholar 

  15. Rodriguez, J. et al. Activity of CeOx and TiOx nanoparticles grown on Au (111) in the water-gas shift reaction. Science 318, 1757–1760 (2007).

    Article  Google Scholar 

  16. Henderson, M. A. The interaction of water with solid surfaces: fundamental aspects revisited. Surf. Sci. Rep. 46, 1–308 (2002).

    Article  Google Scholar 

  17. Huang, W. et al. Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum–nickel hydroxide–graphene. Nat. Commun. 6, 10035 (2015).

    Article  Google Scholar 

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

    Article  Google Scholar 

  19. Gong, M. et al. Blending Cr2O3 into a NiO–Ni electrocatalyst for sustained water splitting. Angew. Chem. Int. Ed. 54, 11989–11993 (2015).

    Article  Google Scholar 

  20. Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I. & Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006).

    Article  Google Scholar 

  21. Park, D., Yun, Y.-S. & Park, J. M. XAS and XPS studies on chromium-binding groups of biomaterial during Cr(VI) biosorption. J. Colloid. Interface Sci. 317, 54–61 (2008).

    Article  Google Scholar 

  22. Anspoks, A. & Kuzmin, A. Interpretation of the Ni K-edge EXAFS in nanocrystalline nickel oxide using molecular dynamics simulations. J. Non-Cryst. Solids 357, 2604–2610 (2011).

    Article  Google Scholar 

  23. Grundner, S. et al. Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nat. Commun. 6, 7546 (2015).

    Article  Google Scholar 

  24. Grass, M. E. et al. New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2. Rev. Sci. Instrum. 81, 053106 (2010).

    Article  Google Scholar 

  25. Callejas, J. F. et al. Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles. ACS Nano 8, 11101–11107 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  29. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558 (1993).

    Article  Google Scholar 

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

    Article  MathSciNet  Google Scholar 

  31. Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the stability of nickel oxide: An LSDA + U study. Phys. Rev. B 57, 1505 (1998).

    Article  Google Scholar 

  32. Jain, A. et al. Formation enthalpies by mixing GGA and GGA+U calculations. Phys. Rev. B 84, 045115 (2011).

    Article  Google Scholar 

  33. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901 (2000).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Ontario Research Fund: Research Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada, and the Connaught Global Challenge programme of the University of Toronto. F.P.G.d.A. acknowledges financial support from the Connaught Fund. P.D.L acknowledges financial support from NSERC in the form of the Canada Graduate Scholarship – Doctoral (CGS-D) award. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. This research also used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory and was supported by the US DOE under contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP). SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada Ltd., Ontario Centres of Excellence, Mitacs, and 15 Ontario academic member institutions.

Author information

Author notes

  1. These authors contributed equally: Cao-Thang Dinh, Ankit Jain, F. Pelayo García de Arquer.

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Cao-Thang Dinh, Ankit Jain, F. Pelayo García de Arquer, Phil De Luna, Jun Li, Ning Wang, Xueli Zheng, Oleksandr Voznyy, Bo Zhang, Min Liu & Edward H. Sargent

  2. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    Jun Li & David Sinton

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Jun Cai, Benjamin Z. Gregory & Ethan J. Crumlin

Authors
  1. Cao-Thang Dinh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ankit Jain
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F. Pelayo García de Arquer
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Phil De Luna
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jun Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ning Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Xueli Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jun Cai
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Benjamin Z. Gregory
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Oleksandr Voznyy
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Bo Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Min Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. David Sinton
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Ethan J. Crumlin
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Edward H. Sargent
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

E.H.S. supervised the project. C.-T.D. and F.P.G.d.A. designed and carried out the experiments. A.J. carried out the DFT calculation. J.C., B.Z.G. and E.J.C. performed the AP-XPS measurements. J.L. performed the XAS measurements. C.-T.D., A.J., F.P.G.d.A. and E.H.S. wrote the manuscript. All the authors discussed the results and assisted during the manuscript preparation.

Corresponding author

Correspondence to Edward H. Sargent.

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 1–11, Supplementary Tables 1–3, Supplementary References

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dinh, CT., Jain, A., de Arquer, F.P.G. et al. Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules. Nat Energy 4, 107–114 (2019). https://doi.org/10.1038/s41560-018-0296-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-018-0296-8

This article is cited by

Search

Advanced 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