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:

Gold-supported cerium-doped NiOx catalysts for water oxidation

Abstract

The development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiOx films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeOx–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highly active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeOx–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.

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

Access options

Buy this article

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

Figure 1: Physical and chemical characterization of NiCeOx–Au.
Figure 2: Experimental and theoretical OER performance of NiCeOx–Au.
Figure 3: Deconvolution of the various effects modifying the OER performance of NiCeOx–Au.
Figure 4: Evaluation of the performance of NiCeOx–Au in an electrolyser set-up.

Similar content being viewed by others

References

  1. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nature Mater. 11, 19–29 (2012).

    Article  Google Scholar 

  2. Dunn, B., Kamath, H. & Tarascon, J.-M. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).

    Article  Google Scholar 

  3. Khaselev, O. & Turner, J. A. A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting. Science 280, 425–427 (1998).

    Article  Google Scholar 

  4. Desmond Ng, J. W., Gorlin, Y., Hatsukade, T. & Jaramillo, T. F. A precious-metal-free regenerative fuel cell for storing renewable electricity. Adv. Energy Mater. 3, 1545–1550 (2013).

    Article  Google Scholar 

  5. Yang, Z. et al. Electrochemical energy storage for green grid. Chem. Rev. 111, 3577–3613 (2011).

    Article  Google Scholar 

  6. Hong, W. T. et al. Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis. Energy Environ. Sci. 8, 1404–1427 (2015).

    Article  Google Scholar 

  7. Vesborg, P. C. & Jaramillo, T. F. Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy. RSC Adv. 2, 7933–7947 (2012).

    Article  Google Scholar 

  8. Haber, J. A. et al. Discovering Ce-rich oxygen evolution catalysts, from high throughput screening to water electrolysis. Energy Environ. Sci. 7, 682–688 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  10. Galán-Mascarós, J. R. Water oxidation at electrodes modified with earth-abundant transition-metal catalysts. ChemElectroChem 2, 37–50 (2015).

    Article  Google Scholar 

  11. Ng, J. W. D., Tang, M. & Jaramillo, T. F. A carbon-free, precious-metal-free, high-performance O2 electrode for regenerative fuel cells and metal–air batteries. Energy Environ. Sci. 7, 2017–2024 (2014).

    Article  Google Scholar 

  12. Suntivich, J., May, K. J., Gasteiger, H. A., Goodenough, J. B. & Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011).

    Article  Google Scholar 

  13. Greeley, J. & Markovic, N. M. The road from animal electricity to green energy: combining experiment and theory in electrocatalysis. Energy Environ. Sci. 5, 9246–9256 (2012).

    Article  Google Scholar 

  14. Klingan, K. et al. Water oxidation by amorphous cobalt-based oxides: volume activity and proton transfer to electrolyte bases. ChemSusChem 7, 1301–1310 (2014).

    Article  Google Scholar 

  15. Gerken, J. B., Shaner, S. E., Masse, R. C., Porubsky, N. J. & Stahl, S. S. A survey of diverse earth abundant oxygen evolution electrocatalysts showing enhanced activity from Ni-Fe oxides containing a third metal. Energy Environ. Sci. 7, 2376–2382 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  17. Gul, S. et al. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry. Phys. Chem. Chem. Phys. 17, 8901–8912 (2015).

    Article  Google Scholar 

  18. Lu, X. & Zhao, C. Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities. Nature Commun. 6, 6616 (2015).

    Article  Google Scholar 

  19. Smith, R. D. et al. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis. Science 340, 60–63 (2013).

    Article  Google Scholar 

  20. Corrigan, D. A. & Bendert, R. M. Effect of coprecipitated metal ions on the electrochemistry of nickel hydroxide thin films: cyclic voltammetry in 1M KOH. J. Electrochem. Soc. 136, 723–728 (1989).

    Article  Google Scholar 

  21. Louie, M. W. & Bell, A. T. An investigation of thin-film Ni–Fe oxide catalysts for the electrochemical evolution of oxygen. J. Am. Chem. Soc. 135, 12329–12337 (2013).

    Article  Google Scholar 

  22. Yeo, B. S. & Bell, A. T. In situ Raman study of nickel oxide and gold-supported nickel oxide catalysts for the electrochemical evolution of oxygen. J. Phys. Chem. C 116, 8394–8400 (2012).

    Article  Google Scholar 

  23. Yeo, B. S. & Bell, A. T. Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen. J. Am. Chem. Soc. 133, 5587–5593 (2011).

    Article  Google Scholar 

  24. Gorlin, Y. et al. Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation. J. Am. Chem. Soc. 136, 4920–4926 (2014).

    Article  Google Scholar 

  25. Frydendal, R. et al. Enhancing activity for the oxygen evolution reaction: the beneficial interaction of gold with manganese and cobalt oxides. ChemCatChem 7, 149–154 (2015).

    Article  Google Scholar 

  26. McCrory, C. C. L. et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am. Chem. Soc. 137, 4347–4357 (2015).

    Article  Google Scholar 

  27. Burke, M. S., Kast, M. G., Trotochaud, L., Smith, A. M. & Boettcher, S. W. Cobalt–iron (oxy)hydroxide oxygen evolution electrocatalysts: the role of structure and composition on activity, stability, and mechanism. J. Am. Chem. Soc. 137, 3638–3648 (2015).

    Article  Google Scholar 

  28. Trotochaud, L., Young, S. L., Ranney, J. K. & Boettcher, S. W. Nickel–iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 136, 6744–6753 (2014).

    Article  Google Scholar 

  29. Friebel, D. et al. Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. J. Am. Chem. Soc. 137, 1305–1313 (2015).

    Article  Google Scholar 

  30. Klaus, S., Cai, Y., Louie, M. W., Trotochaud, L. & Bell, A. T. Effects of Fe electrolyte impurities on Ni(OH)2/NiOOH structure and oxygen evolution activity. J. Phys. Chem. C 119, 7243–7254 (2015).

    Article  Google Scholar 

  31. Zou, S. et al. Fe (Oxy)hydroxide oxygen evolution reaction electrocatalysis: intrinsic activity and the roles of electrical conductivity, substrate, and dissolution. Chem. Mater. 27, 8011–8020 (2015).

    Article  Google Scholar 

  32. Grosvenor, A. P., Biesinger, M. C., Smart, R. S. C. & McIntyre, N. S. New interpretations of XPS spectra of nickel metal and oxides. Surf. Sci. 600, 1771–1779 (2006).

    Article  Google Scholar 

  33. McIntyre, N. S. & Cook, M. G. X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper. Anal. Chem. 47, 2208–2213 (1975).

    Article  Google Scholar 

  34. Stefanov, P., Atanasova, G., Stoychev, D. & Marinova, T. Electrochemical deposition of CeO2 on ZrO2 and Al2O3 thin films formed on stainless steel. Surf. Coat. Tech. 180–181, 446–449 (2004).

    Article  Google Scholar 

  35. Yu, X. & Li, G. XPS study of cerium conversion coating on the anodized 2024 aluminum alloy. J. Alloy. Compd. 364, 193–198 (2004).

    Article  Google Scholar 

  36. Batchellor, A. S. & Boettcher, S. W. Pulse-electrodeposited Ni–Fe (oxy)hydroxide oxygen evolution electrocatalysts with high geometric and intrinsic activities at large mass loadings. ACS Catal. 5, 6680–6689 (2015).

    Article  Google Scholar 

  37. Man, I. C. et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011).

    Article  Google Scholar 

  38. Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Article  Google Scholar 

  39. Li, Y.-F. & Selloni, A. Mechanism and activity of water oxidation on selected surfaces of pure and Fe-doped NiOx . ACS Catal. 4, 1148–1153 (2014).

    Article  Google Scholar 

  40. Strmcnik, D. et al. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nature Chem. 5, 300–306 (2013).

    Article  Google Scholar 

  41. Vojvodic, A. & Nørskov, J. K. New design paradigm for heterogeneous catalysts. Natl Sci. Rev. 2, 140–149 (2015).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  44. 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).

    Article  Google Scholar 

  45. 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).

    Article  Google Scholar 

  46. Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys. Rev. B 57, 1505–1509 (1998).

    Article  Google Scholar 

  47. Jain, A. et al. Commentary: the materials project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).

    Article  Google Scholar 

  48. Fabris, S., de Gironcoli, S., Baroni, S., Vicario, G. & Balducci, G. Taming multiple valency with density functionals: a case study of defective ceria. Phys. Rev. B 71, 041102 (2005).

    Article  Google Scholar 

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

    Article  MathSciNet  Google Scholar 

  50. Walton, A. S. et al. Interface controlled oxidation states in layered cobalt oxide nanoislands on gold. ACS Nano 9, 2445–2453 (2015).

    Article  Google Scholar 

  51. Rossmeisl, J., Logadottir, A. & Nørskov, J. K. Electrolysis of water on (oxidized) metal surfaces. Chem. Phys. 319, 178–184 (2005).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0008685 and the US Department of Energy Office of Basic Energy Science grant to the SUNCAT Center for Interface Science and Catalysis. Partial support to initiate the project was provided as part of the Center on Nanostructuring for Efficient Energy Conversion (CNEEC) at Stanford University, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001060. The authors would like to thank L. Seitz for helpful discussions and R. Kravec for help with XRD measurements. J.W.D.N. acknowledges funding from the Agency of Science, Technology, and Research (ASTAR), Singapore. M.G.-M. acknowledges funding from the Agency for Administration of University and Research Grants of Catalonia (AGAUR, 2013 BP-A 00464). C.K. acknowledges funding from the Stanford Graduate Fellowship. A.V. acknowledges funding through the SLAC National Accelerator Laboratory LDRD Program.

Author information

Authors and Affiliations

Authors

Contributions

J.W.D.N. and T.F.J. conceived and designed the experiments. J.W.D.N., P.C. and C.K. carried out material synthesis. J.W.D.N. and P.C. performed physical and chemical characterization. J.W.D.N., P.C. and C.K. conducted the electrochemical measurements. M.G.-M., M.B. and A.V. formulated, defined and designed the computational part of the paper. M.G.-M. and M.B. performed all the DFT calculations under supervision from A.V. All authors discussed the results and co-wrote the paper.

Corresponding authors

Correspondence to Aleksandra Vojvodic or Thomas F. Jaramillo.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information.

Supplementary Figures 1–13, Supplementary Table 1, Supplementary Discussion and Supplementary References. (PDF 2277 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ng, J., García-Melchor, M., Bajdich, M. et al. Gold-supported cerium-doped NiOx catalysts for water oxidation. Nat Energy 1, 16053 (2016). https://doi.org/10.1038/nenergy.2016.53

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/nenergy.2016.53

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