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.

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References

  1. 1.

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

  2. 2.

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

  3. 3.

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

  4. 4.

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

  5. 5.

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

  6. 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).

  7. 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).

  8. 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).

  9. 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).

  10. 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).

  11. 11.

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

  12. 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).

  13. 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).

  14. 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).

  15. 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).

  16. 16.

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

  17. 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).

  18. 18.

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

  19. 19.

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

  20. 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).

  21. 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).

  22. 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).

  23. 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).

  24. 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).

  25. 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).

  26. 26.

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

  27. 27.

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

  28. 28.

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

  29. 29.

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

  30. 30.

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

  31. 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).

  32. 32.

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

  33. 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).

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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.

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

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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.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Edward H. Sargent.

Supplementary information

  1. Supplementary Information

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

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

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