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
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
All data are available from the corresponding author on reasonable request.
References
Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).
Cook, T. R. et al. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 110, 6474–6502 (2010).
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).
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).
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).
Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).
Matsumoto, Y. & Sato, E. Electrocatalytic properties of transition metal oxides for oxygen evolution reaction. Mater. Chem. Phys. 14, 397–426 (1986).
Gong, M. et al. An advanced Ni–Fe layered double hydroxide electrocatalyst for water oxidation. J. Am. Chem. Soc. 135, 8452–8455 (2013).
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).
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).
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).
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).
Dionigi, F. & Strasser, P. NiFe-based (oxy)hydroxide catalysts for oxygen evolution reaction in non-acidic electrolytes. Adv. Energy Mater. 6, 1600621 (2016).
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).
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).
Colli, A. N., Girault, H. H. & Battistel, A. Non-precious electrodes for practical alkaline water electrolysis. Materials 12, 1336 (2019).
Brauns, J. & Turek, T. Alkaline water electrolysis powered by renewable energy: a review. Processes 8, 248 (2020).
Marini, S. et al. Advanced alkaline water electrolysis. Electrochim. Acta 82, 384–391 (2012).
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).
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).
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).
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).
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).
Schäfer, H. et al. Stainless steel made to rust: a robust water-splitting catalyst with benchmark characteristics. Energy Environ. Sci. 8, 2685–2697 (2015).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
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).
McIntyre, N. S. & Zetaruk, D. G. X-ray photoelectron spectroscopic studies of iron oxides. Anal. Chem. 49, 1521–1529 (1977).
Asami, K. & Hashimoto, K. The X-ray photo-electron spectra of several oxides of iron and chromium. Corros. Sci. 17, 559–570 (1977).
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).
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).
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).
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).
Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous Solutions (National Association of Corrosion Engineers, 1979).
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).
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).
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).
Liu, X. et al. Metal (Ni, Co)-metal oxides/graphene nanocomposites as multifunctional electrocatalysts. Adv. Funct. Mater. 25, 5799–5808 (2015).
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).
Rauch, E. F. & Véron, M. Automated crystal orientation and phase mapping in TEM. Mater. Charact. 98, 1–9 (2014).
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).
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).
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).
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
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
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.
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.
About this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-023-01744-5