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:

Fe–Ni-based alloys as highly active and low-cost oxygen evolution reaction catalyst in alkaline media

Nature Materials volume 23, pages 252–261 (2024)Cite this article

Subjects

Abstract

NiFe-based oxo-hydroxides are highly active for the oxygen evolution reaction but require complex synthesis and are poorly durable when deposited on foreign supports. Herein we demonstrate that easily processable, Earth-abundant and cheap Fe–Ni alloys spontaneously develop a highly active NiFe oxo-hydroxide surface, exsolved upon electrochemical activation. While the manufacturing process and the initial surface state of the alloys do not impact the oxygen evolution reaction performance, the growth/composition of the NiFe oxo-hydroxide surface layer depends on the alloying elements and initial atomic Fe/Ni ratio, hence driving oxygen evolution reaction activity. Whatever the initial Fe/Ni ratio of the Fe–Ni alloy (varying between 0.004 and 7.4), the best oxygen evolution reaction performance (beyond that of commercial IrO2) and durability was obtained for a surface Fe/Ni ratio between 0.2 and 0.4 and includes numerous active sites (high NiIII/NiII capacitive response) and high efficiency (high Fe/Ni ratio). This knowledge paves the way to active and durable Fe–Ni alloy oxygen-evolving electrodes for alkaline water electrolysers.

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: Electrochemical characterization of OER performance in 0.1 M KOH at 25 °C.
Fig. 2: Microstructural characterization of the active surface layer.
Fig. 3: TEM-EDS analysis: chemical composition profiles performed on samples after activations.
Fig. 4: XPS spectra deconvolution of Ni, Fe and Cr peaks.
Fig. 5: Key electrochemical parameters affected by the active-surface-layer chemical composition.

Similar content being viewed by others

Data availability

All data are available from the corresponding author on reasonable request.

References

  1. Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).

    Article  CAS  Google Scholar 

  2. Cook, T. R. et al. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 110, 6474–6502 (2010).

    Article  CAS  Google Scholar 

  3. Jiao, Y., Zheng, Y., Jaroniec, M. & Qiao, S. Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 44, 2060–2086 (2015).

    Article  CAS  Google Scholar 

  4. Ayers, K. et al. Perspectives on low-temperature electrolysis and potential for renewable hydrogen at scale. Annu. Rev. Chem. Biomol. Eng. 10, 219–239 (2019).

    Article  CAS  Google Scholar 

  5. McCrory, C. C. L., Jung, S., Peters, J. C. & Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 135, 16977–16987 (2013).

    Article  CAS  Google Scholar 

  6. Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).

    Article  CAS  Google Scholar 

  7. Matsumoto, Y. & Sato, E. Electrocatalytic properties of transition metal oxides for oxygen evolution reaction. Mater. Chem. Phys. 14, 397–426 (1986).

    Article  CAS  Google Scholar 

  8. Gong, M. et al. An advanced Ni–Fe layered double hydroxide electrocatalyst for water oxidation. J. Am. Chem. Soc. 135, 8452–8455 (2013).

    Article  CAS  Google Scholar 

  9. 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  CAS  Google Scholar 

  10. Trotochaud, L., Ranney, J. K., Williams, K. N. & Boettcher, S. W. Solution-cast metal oxide thin film electrocatalysts for oxygen evolution. J. Am. Chem. Soc. 134, 17253–17261 (2012).

    Article  CAS  Google Scholar 

  11. 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  CAS  Google Scholar 

  12. Corrigan, D. A. The catalysis of the oxygen evolution reaction by iron impurities in thin film nickel oxide electrodes. J. Electrochem. Soc. 134, 377–384 (1987).

    Article  CAS  Google Scholar 

  13. Dionigi, F. & Strasser, P. NiFe-based (oxy)hydroxide catalysts for oxygen evolution reaction in non-acidic electrolytes. Adv. Energy Mater. 6, 1600621 (2016).

    Article  Google Scholar 

  14. Görlin, M. et al. Oxygen evolution reaction dynamics, faradaic charge efficiency, and the active metal redox states of Ni–Fe oxide water splitting electrocatalysts. J. Am. Chem. Soc. 138, 5603–5614 (2016).

    Article  Google Scholar 

  15. Song, F. et al. Transition metal oxides as electrocatalysts for the oxygen evolution reaction in alkaline solutions: an application-inspired renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018).

    Article  CAS  Google Scholar 

  16. Colli, A. N., Girault, H. H. & Battistel, A. Non-precious electrodes for practical alkaline water electrolysis. Materials 12, 1336 (2019).

    Article  CAS  Google Scholar 

  17. Brauns, J. & Turek, T. Alkaline water electrolysis powered by renewable energy: a review. Processes 8, 248 (2020).

    Article  CAS  Google Scholar 

  18. Marini, S. et al. Advanced alkaline water electrolysis. Electrochim. Acta 82, 384–391 (2012).

    Article  CAS  Google Scholar 

  19. 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  CAS  Google Scholar 

  20. 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  CAS  Google Scholar 

  21. Enman, L. J., Burke, M. S., Batchellor, A. S. & Boettcher, S. W. Effects of intentionally incorporated metal cations on the oxygen evolution electrocatalytic activity of nickel (oxy)hydroxide in alkaline media. ACS Catal. 6, 2416–2423 (2016).

    Article  CAS  Google Scholar 

  22. Mirabella, F. et al. Ni-modified Fe3O4(001) surface as a simple model system for understanding the oxygen evolution reaction. Electrochim. Acta 389, 138638 (2021).

    Article  CAS  Google Scholar 

  23. Wang, L. et al. Deciphering the exceptional performance of NiFe hydroxide for the oxygen evolution reaction in an anion exchange membrane electrolyzer. ACS Appl. Energy Mater. 5, 2221–2230 (2022).

    Article  CAS  Google Scholar 

  24. Schäfer, H. et al. Stainless steel made to rust: a robust water-splitting catalyst with benchmark characteristics. Energy Environ. Sci. 8, 2685–2697 (2015).

    Article  Google Scholar 

  25. Diaz-Morales, O., Ferrus-Suspedra, D. & Koper, M. T. M. The importance of nickel oxyhydroxide deprotonation on its activity towards electrochemical water oxidation. Chem. Sci. 7, 2639–2645 (2016).

    Article  CAS  Google Scholar 

  26. Qiu, Z., Tai, C.-W., Niklasson, G. A. & Edvinsson, T. Direct observation of active catalyst surface phases and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting. Energy Environ. Sci. 12, 572–581 (2019).

    Article  CAS  Google Scholar 

  27. Burke, M. S., Enman, L. J., Batchellor, A. S., Zou, S. & Boettcher, S. W. Oxygen evolution reaction electrocatalysis on transition metal oxides and (oxy)hydroxides: activity trends and design principles. Chem. Mater. 27, 7549–7558 (2015).

    Article  CAS  Google Scholar 

  28. Spöri, C., Kwan, J. T. H., Bonakdarpour, A., Wilkinson, D. P. & Strasser, P. The stability challenges of oxygen evolving catalysts: towards a common fundamental understanding and mitigation of catalyst degradation. Angew. Chem. Int. Ed. 56, 5994–6021 (2017).

    Article  Google Scholar 

  29. Maljusch, A., Conradi, O., Hoch, S., Blug, M. & Schuhmann, W. Advanced evaluation of the long-term stability of oxygen evolution electrocatalysts. Anal. Chem. 88, 7597–7602 (2016).

    Article  CAS  Google Scholar 

  30. Zeradjanin, A. R. et al. Rational design of the electrode morphology for oxygen evolution – enhancing the performance for catalytic water oxidation. RSC Adv. 4, 9579–9587 (2014).

    Article  CAS  Google Scholar 

  31. Andronescu, C. et al. Powder catalyst fixation for post-electrolysis structural characterization of NiFe layered double hydroxide based oxygen evolution reaction electrocatalysts. Angew. Chem. Int. Ed. 56, 11258–11262 (2017).

    Article  CAS  Google Scholar 

  32. Lafforgue, C., Maillard, F., Martin, V., Dubau, L. & Chatenet, M. Degradation of carbon-supported platinum-group-metal electrocatalysts in alkaline media studied by in situ Fourier transform infrared spectroscopy and identical-location transmission electron microscopy. ACS Catal. 9, 5613–5622 (2019).

    Article  CAS  Google Scholar 

  33. Möller, S. et al. Online monitoring of electrochemical carbon corrosion in alkaline electrolytes by differential electrochemical mass spectrometry. Angew. Chem. Int. Ed. 59, 1585–1589 (2020).

    Article  Google Scholar 

  34. Moureaux, F., Stevens, P., Toussaint, G. & Chatenet, M. Development of an oxygen-evolution electrode from 316L stainless steel: application to the oxygen evolution reaction in aqueous lithium–air batteries. J. Power Sources 229, 123–132 (2013).

    Article  CAS  Google Scholar 

  35. Moureaux, F., Stevens, P., Toussaint, G. & Chatenet, M. Timely-activated 316L stainless steel: a low cost, durable and active electrode for oxygen evolution reaction in concentrated alkaline environments. Appl. Catal. B Environ. 258, 117963 (2019).

    Article  CAS  Google Scholar 

  36. Todoroki, N. & Wadayama, T. Heterolayered Ni–Fe hydroxide/oxide nanostructures generated on a stainless-steel substrate for efficient alkaline water splitting. ACS Appl. Mater. Interfaces 11, 44161–44169 (2019).

    Article  CAS  Google Scholar 

  37. Todoroki, N., Shinomiya, A. & Wadayama, T. Nanostructures and oxygen evolution overpotentials of surface catalyst layers synthesized on various austenitic stainless steel electrodes. Electrocatalysis 13, 116–125 (2022).

    Article  CAS  Google Scholar 

  38. Kostecki, R. & McLarnon, F. Electrochemical and in situ raman spectroscopic characterization of nickel hydroxide electrodes: I. Pure nickel hydroxide. J. Electrochem. Soc. 144, 485–493 (1997).

    Article  CAS  Google Scholar 

  39. Lyons, M. E. & Brandon, M. P. The oxygen evolution reaction on passive oxide covered transition metal electrodes in aqueous alkaline solution. Part 1-Nickel. Int. J. Electrochem. Sci. 3, 1386–1424 (2008).

    Article  CAS  Google Scholar 

  40. Li, X., Walsh, F. C. & Pletcher, D. Nickel based electrocatalysts for oxygen evolution in high current density, alkaline water electrolysers. Phys. Chem. Chem. Phys. 13, 1162–1167 (2011).

    Article  CAS  Google Scholar 

  41. Chung, D. Y. et al. Dynamic stability of active sites in hydr(oxy)oxides for the oxygen evolution reaction. Nat. Energy 5, 222–230 (2020).

    Article  Google Scholar 

  42. Todoroki, N. & Wadayama, T. Electrochemical stability of stainless-steel-made anode for alkaline water electrolysis: surface catalyst nanostructures and oxygen evolution overpotentials under applying potential cycle loading. Electrochem. Commun. 122, 106902 (2021).

    Article  CAS  Google Scholar 

  43. Todoroki, N. & Wadayama, T. Dissolution of constituent elements from various austenitic stainless steel oxygen evolution electrodes under potential cycle loadings. Int. J. Hydrog. Energy 47, 32753–32762 (2022).

    Article  CAS  Google Scholar 

  44. Neagu, D. et al. In situ observation of nanoparticle exsolution from perovskite oxides: from atomic scale mechanistic insight to nanostructure tailoring. ACS Nano 13, 12996–13005 (2019).

    Article  CAS  Google Scholar 

  45. Ali-Löytty, H. et al. Ambient-pressure XPS study of a Ni–Fe electrocatalyst for the oxygen evolution reaction. J. Phys. Chem. C 120, 2247–2253 (2016).

    Article  Google Scholar 

  46. Biesinger, M. C. et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 257, 2717–2730 (2011).

    Article  CAS  Google Scholar 

  47. McIntyre, N. S. & Zetaruk, D. G. X-ray photoelectron spectroscopic studies of iron oxides. Anal. Chem. 49, 1521–1529 (1977).

    Article  CAS  Google Scholar 

  48. Asami, K. & Hashimoto, K. The X-ray photo-electron spectra of several oxides of iron and chromium. Corros. Sci. 17, 559–570 (1977).

    Article  CAS  Google Scholar 

  49. Balasubramanian, M., Melendres, C. A. & Mini, S. X-ray absorption spectroscopy studies of the local atomic and electronic structure of iron incorporated into electrodeposited hydrous nickel oxide films. J. Phys. Chem. B 104, 4300–4306 (2000).

    Article  CAS  Google Scholar 

  50. Smith, R. D. L. et al. Geometric distortions in nickel (oxy)hydroxide electrocatalysts by redox inactive iron ions. Energy Environ. Sci. 11, 2476–2485 (2018).

    Article  CAS  Google Scholar 

  51. Bajdich, M., García-Mota, M., Vojvodic, A., Nørskov, J. K. & Bell, A. T. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. J. Am. Chem. Soc. 135, 13521–13530 (2013).

    Article  CAS  Google Scholar 

  52. Poulain, R., Klein, A. & Proost, J. Electrocatalytic properties of (100)-, (110)-, and (111)-oriented NiO thin films toward the oxygen evolution reaction. J. Phys. Chem. C 122, 22252–22263 (2018).

    Article  CAS  Google Scholar 

  53. Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous Solutions (National Association of Corrosion Engineers, 1979).

  54. Xiang, Q. et al. In situ vertical growth of Fe–Ni layered double-hydroxide arrays on Fe–Ni alloy foil: interfacial layer enhanced electrocatalyst with small overpotential for oxygen evolution reaction. ACS Energy Lett. 3, 2357–2365 (2018).

    Article  CAS  Google Scholar 

  55. Dionigi, F. et al. In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution. Nat. Commun. 11, 2522 (2020).

    Article  CAS  Google Scholar 

  56. Han, W. et al. Free‐sustaining three‐dimensional S235 steel‐based porous electrocatalyst for highly efficient and durable oxygen evolution. Chem. Sus. Chem. 11, 3661–3671 (2018).

    Article  CAS  Google Scholar 

  57. Liu, X. et al. Metal (Ni, Co)-metal oxides/graphene nanocomposites as multifunctional electrocatalysts. Adv. Funct. Mater. 25, 5799–5808 (2015).

    Article  CAS  Google Scholar 

  58. Dionigi, F. et al. Intrinsic electrocatalytic activity for oxygen evolution of crystalline 3D‐transition metal layered double hydroxides. Angew. Chem. Int. Ed. 133, 14567–14578 (2021).

    Article  Google Scholar 

  59. Rauch, E. F. & Véron, M. Automated crystal orientation and phase mapping in TEM. Mater. Charact. 98, 1–9 (2014).

    Article  CAS  Google Scholar 

  60. Fujita, S. et al. The effect of LixNi2–xO2/Ni with modification method on activity and durability of alkaline water electrolysis anode. Electrocatalysis 9, 162–171 (2018).

  61. Chatenet, M. et al. Electrochemical measurement of the oxygen diffusivity and solubility in concentrated alkaline media on rotating ring-disk and disk electrodes—application to industrial chlorine-soda electrolyte. Electrochim. Acta 45, 2823–2827 (2000).

    Article  CAS  Google Scholar 

  62. Chatenet, M. et al. Direct rotating ring-disk measurement of the sodium borohydride diffusion coefficient in sodium hydroxide solutions. Electrochim. Acta 54, 4426–4435 (2009).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was funded by Carnot EF (NICKEL project, L.M., V.R., C.P., E.S., V.P. and M.C.). V.P., V.R., M.C. and E.S. thank P. Joncourt and W. Ait Idir, who participated in a preliminary study that ended up in this project. The research has benefited from the characterization equipment of the Grenoble INP – CMTC platform supported by the Centre of Excellence of Multifunctional Architectured Materials ‘CEMAM’ (grant ANR-10-LABX-44-01) funded by the ‘Investments for the Future’ programme (L.M., G.C., V.M., V.R., C.P., E.S., V.P. and M.C.). We thank G. Berthomé for the XPS measurements, G. Renou for the TEM analysis and S. Coindeau and T. Encinas for XRD measurements. The internship of G.C. was funded by the DAEMONHYC project, supported by the ‘France 2030’ government investment plan managed by the French National Research Agency, under reference ‘ANR-22-PEHY-0010’ (G.C., E.S. and M.C.).

Author information

Authors and Affiliations

  1. Univ. Grenoble Alpes, CNRS, Grenoble INP (Institute of Engineering, Univ. Grenoble Alpes), SIMAP, Grenoble, France

    Lucile Magnier, Céline Pascal & Valérie Parry

  2. Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP (Institute of Engineering, Univ. Grenoble Alpes), LEPMI, Grenoble, France

    Lucile Magnier, Garance Cossard, Vincent Martin, Virginie Roche, Eric Sibert & Marian Chatenet

  3. Pierre Chevenard Research Center, APERAM Alloys Imphy, Imphy, France

    Irina Shchedrina

  4. Product Development, APERAM Alloys Imphy, Imphy, France

    Richard Bousquet

Authors
  1. Lucile Magnier
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Garance Cossard
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vincent Martin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Céline Pascal
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Virginie Roche
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Eric Sibert
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Irina Shchedrina
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Richard Bousquet
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Valérie Parry
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Marian Chatenet
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

C.P., V.R., E.S., V.P. and M.C. designed the project study. I.S. and R.B. provided the samples. L.M. carried out the experiments and analysed the data, except for the following: G.C. and M.C. performed the rotating ring-disc experiments and evaluated the corresponding OER faradaic efficiency; G.C. performed the accelerated stress tests; and V.M. performed the ICP-MS measurements to evaluate the extent of metal dissolution upon OER. C.P., V.R., E.S., V.P., I.S., R.B. and M.C. helped in discussing the results. All authors contributed to the preparation of the manuscript.

Corresponding author

Correspondence to Marian Chatenet.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks Helmut Schäfer and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Electrochemical characterization of IrO2 with two loadings: 20 µg.cm−2 and 100 µg.cm−2.

The CV scans are performed at 50 mV.s−1. The start of the CVs is indicated by the dot and the scan direction by the arrows.

Extended Data Fig. 2 TEM analysis of W-718 after activations.

(a) Diffraction pattern in a well-crystallized zone in the active-surface layer. (b) Correspondence between the cubic NiO phase (green circles) and the diffraction pattern of (a).

Extended Data Fig. 3 Image of wires and plates.

(a) after cutting, (b) placed in the sample holders.

Extended Data Fig. 4 Influence of the scan rate.

(a) CV scan at different scan rates on P-825 after activations. (b) Potential at a current density of 5 mA.cm−2 reported from the CV scans at different scan rates. The scan rate has a minimal impact on the potential measured at a current density of 5 mA cm−2 (one of the activity markers considered in this study); the potential only varies by a few mV depending on the scan rate, which overall denotes for the minimal impact of the potential scan rate with the kinetic markers chosen herein. This is ascribed to the fact that (i) only smooth polished surfaces were tested (this was deliberate, so to minimize the capacitive behaviour of the electrodes) and (ii) they display very high faradaic OER activity; as a result, the faradaic contribution overwhelms the capacitive one. 50 mV.s−1 was chosen (20 mV.s−1 in the RRDE experiments), so to limit as much as possible hindrance by the evolved oxygen bubbles, which becomes more prevalent at lower potential scan rate.

Extended Data Table 1 Details of the main characteristics of the different grades supplied by Aperam company and the pure Ni (Alfa Aesar, 99.999%)
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–9, Tables 1 and 2 and Discussion.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Magnier, L., Cossard, G., Martin, V. et al. Fe–Ni-based alloys as highly active and low-cost oxygen evolution reaction catalyst in alkaline media. Nat. Mater. 23, 252–261 (2024). https://doi.org/10.1038/s41563-023-01744-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-023-01744-5

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