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:

Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis

Nature Materials volume 22, pages 100–108 (2023)Cite this article

Subjects

Abstract

Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO2) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm−2, suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO2, as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.

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: Synthesis and characterization of Ni-RuO2.
Fig. 2: Electronic structure of Ni-RuO2 and RuO2.
Fig. 3: Acidic OER performance on RDE.
Fig. 4: Understanding the mechanism.
Fig. 5: PEM–WE device performance using Ni-RuO2 as an acidic OER catalyst at room temperature and ambient pressure.

Similar content being viewed by others

Data availability

The data that support the findings of this study are presented in the main text and the Supplementary Information, and are available from the corresponding authors upon reasonable request.

References

  1. Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).

    Article  CAS  Google Scholar 

  2. Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).

    Article  CAS  Google Scholar 

  3. Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).

    Article  Google Scholar 

  4. Carmo, M., Fritz, D. L., Mergel, J. & Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrog. Energy 38, 4901–4934 (2013).

    Article  CAS  Google Scholar 

  5. An, L. et al. Recent development of oxygen evolution electrocatalysts in acidic environment. Adv. Mater. 33, 2006328 (2021).

    Article  CAS  Google Scholar 

  6. 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. Engl. 56, 5994–6021 (2017).

    Article  Google Scholar 

  7. King, L. A. et al. A non-precious metal hydrogen catalyst in a commercial polymer electrolyte membrane electrolyser. Nat. Nanotechnol. 14, 1071–1074 (2019).

    Article  CAS  Google Scholar 

  8. Li, L., Wang, P., Shao, Q. & Huang, X. Recent progress in advanced electrocatalyst design for acidic oxygen evolution reaction. Adv. Mater. 33, e2004243 (2021).

  9. Chen, F.-Y., Wu, Z.-Y., Adler, Z. & Wang, H. Stability challenges of electrocatalytic oxygen evolution reaction: from mechanistic understanding to reactor design. Joule 5, 1704–1731 (2021).

    Article  CAS  Google Scholar 

  10. Seitz, L. C. et al. A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science 353, 1011–1014 (2016).

    Article  CAS  Google Scholar 

  11. Chatti, M. et al. Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 °C. Nat. Catal. 2, 457–465 (2019).

    Article  CAS  Google Scholar 

  12. Yao, Y. et al. Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis. Nat. Catal. 2, 304–313 (2019).

    Article  CAS  Google Scholar 

  13. Wen, Y. et al. Stabilizing highly active Ru sites by suppressing lattice oxygen participation in acidic water oxidation. J. Am. Chem. Soc. 143, 6482–6490 (2021).

    Article  CAS  Google Scholar 

  14. Reier, T. et al. Molecular insight in structure and activity of highly efficient, low-Ir Ir–Ni oxide catalysts for electrochemical water splitting (OER). J. Am. Chem. Soc. 137, 13031–13040 (2015).

    Article  CAS  Google Scholar 

  15. Song, J. et al. A review on fundamentals for designing oxygen evolution electrocatalysts. Chem. Soc. Rev. 49, 2196–2214 (2020).

    Article  CAS  Google Scholar 

  16. Moreno-Hernandez, I. A. et al. Crystalline nickel manganese antimonate as a stable water-oxidation catalyst in aqueous 1.0 M H2SO4. Energy Environ. Sci. 10, 2103–2108 (2017).

    Article  CAS  Google Scholar 

  17. Geiger, S. et al. The stability number as a metric for electrocatalyst stability benchmarking. Nat. Catal. 1, 508–515 (2018).

    Article  CAS  Google Scholar 

  18. Diaz-Morales, O. et al. Iridium-based double perovskites for efficient water oxidation in acid media. Nat. Commun. 7, 12363 (2016).

    Article  CAS  Google Scholar 

  19. Hao, S. et al. Torsion strained iridium oxide for efficient acidic water oxidation in proton exchange membrane electrolyzers. Nat. Nanotechnol. 16, 1371–1377 (2021).

    Article  CAS  Google Scholar 

  20. Zheng, Y.-R. et al. Monitoring oxygen production on mass-selected iridium–tantalum oxide electrocatalysts. Nat. Energy 7, 55–64 (2022).

    Article  CAS  Google Scholar 

  21. Su, J. et al. Assembling ultrasmall copper-doped ruthenium oxide nanocrystals into hollow porous polyhedra: highly robust electrocatalysts for oxygen evolution in acidic media. Adv. Mater. 30, 1801351 (2018).

    Article  Google Scholar 

  22. Retuerto, M. et al. Na-doped ruthenium perovskite electrocatalysts with improved oxygen evolution activity and durability in acidic media. Nat. Commun. 10, 2041 (2019).

    Article  Google Scholar 

  23. Lin, Y. et al. Chromium-ruthenium oxide solid solution electrocatalyst for highly efficient oxygen evolution reaction in acidic media. Nat. Commun. 10, 162 (2019).

    Article  Google Scholar 

  24. Hao, S. et al. Dopants fixation of Ruthenium for boosting acidic oxygen evolution stability and activity. Nat. Commun. 11, 5368 (2020).

    Article  CAS  Google Scholar 

  25. Jin, H. et al. Safeguarding the RuO2 phase against lattice oxygen oxidation during acidic water electrooxidation. Energy Environ. Sci. 15, 1119–1130 (2022).

    Article  CAS  Google Scholar 

  26. Cao, L. et al. Dynamic oxygen adsorption on single-atomic Ruthenium catalyst with high performance for acidic oxygen evolution reaction. Nat. Commun. 10, 4849 (2019).

    Article  Google Scholar 

  27. Chen, S. et al. Mn-doped RuO2 nanocrystals as highly active electrocatalysts for enhanced oxygen evolution in acidic media. ACS Catal. 10, 1152–1160 (2020).

  28. Halck, N. B., Petrykin, V., Krtil, P. & Rossmeisl, J. Beyond the volcano limitations in electrocatalysis – oxygen evolution reaction. Phys. Chem. Chem. Phys. 16, 13682–13688 (2014).

    Article  CAS  Google Scholar 

  29. Wang, J. et al. Transition metal-doped ultrathin RuO2 networked nanowires for efficient overall water splitting across a broad pH range. J. Mater. Chem. A Mater. 7, 6411–6416 (2019).

    Article  CAS  Google Scholar 

  30. Zhao, Z. L. et al. Boosting the oxygen evolution reaction using defect-rich ultra-thin ruthenium oxide nanosheets in acidic media. Energy Environ. Sci. 13, 5143–5151 (2020).

    Article  CAS  Google Scholar 

  31. Hubert, M. A. et al. Acidic oxygen evolution reaction activity–stability relationships in Ru-based pyrochlores. ACS Catal. 10, 12182–12196 (2020).

    Article  CAS  Google Scholar 

  32. Cui, X. et al. Robust interface Ru centers for high-performance acidic oxygen evolution. Adv. Mater. 32, 1908126 (2020).

    Article  CAS  Google Scholar 

  33. Grimaud, A. et al. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat. Chem. 9, 457–465 (2017).

    Article  CAS  Google Scholar 

  34. Wohlfahrt-Mehrens, M. & Heitbaum, J. Oxygen evolution on Ru and RuO2 electrodes studied using isotope labelling and on-line mass spectrometry. J. Electroanal. Chem. Interfacial Electrochem. 237, 251–260 (1987).

    Article  CAS  Google Scholar 

  35. Klyukin, K., Zagalskaya, A. & Alexandrov, V. Role of dissolution intermediates in promoting oxygen evolution reaction at RuO2(110) surface. J. Phys. Chem. C Nanomater. Interfaces 123, 22151–22157 (2019).

    Article  CAS  Google Scholar 

  36. Zagalskaya, A. & Alexandrov, V. Role of defects in the interplay between adsorbate evolving and lattice oxygen mechanisms of the oxygen evolution reaction in RuO2 and IrO2. ACS Catal. 10, 3650–3657 (2020).

    Article  CAS  Google Scholar 

  37. Cherevko, S. Stability and dissolution of electrocatalysts: building the bridge between model and ‘real world’ systems. Curr. Opin. Electrochem. 8, 118–125 (2018).

    Article  CAS  Google Scholar 

  38. Xu, S.-L. et al. High-temperature synthesis of small-sized Pt/Nb alloy catalysts on carbon supports for hydrothermal reactions. Inorg. Chem. 59, 15953–15961 (2020).

    Article  CAS  Google Scholar 

  39. Yu, M. et al. Scalable self-growth of Ni@NiO core-shell electrode with ultrahigh capacitance and super-long cyclic stability for supercapacitors. NPG Asia Mater. 6, e129–e129 (2014).

    Article  CAS  Google Scholar 

  40. Wu, Z.-Y. et al. Partially oxidized Ni nanoparticles supported on Ni-N co-doped carbon nanofibers as bifunctional electrocatalysts for overall water splitting. Nano Energy 51, 286–293 (2018).

    Article  CAS  Google Scholar 

  41. Feng, Q. et al. Highly active and stable ruthenate pyrochlore for enhanced oxygen evolution reaction in acidic medium electrolysis. Appl. Catal. B 244, 494–501 (2019).

    Article  CAS  Google Scholar 

  42. Over, H. Surface chemistry of ruthenium dioxide in heterogeneous catalysis and electrocatalysis: from fundamental to applied research. Chem. Rev. 112, 3356–3426 (2012).

    Article  CAS  Google Scholar 

  43. Rochefort, D., Dabo, P., Guay, D. & Sherwood, P. M. A. XPS investigations of thermally prepared RuO2 electrodes in reductive conditions. Electrochim. Acta 48, 4245–4252 (2003).

    Article  CAS  Google Scholar 

  44. Chen, Y. et al. Exceptionally active iridium evolved from a pseudo-cubic perovskite for oxygen evolution in acid. Nat. Commun. 10, 572 (2019).

    Article  CAS  Google Scholar 

  45. Kim, Y. D., Schwegmann, S., Seitsonen, A. P. & Over, H. Epitaxial growth of RuO2 (100) on Ru (1010): surface structure and other properties. J. Phys. Chem. B 105, 2205–2211 (2001).

    Article  CAS  Google Scholar 

  46. Heras-Domingo, J., Sodupe, M. & Solans-Monfort, X. Interaction between ruthenium oxide surfaces and water molecules. Effect of surface morphology and water coverage. J. Phys. Chem. C Nanometer. Interfaces 123, 7786–7798 (2018).

    Article  Google Scholar 

  47. Rao, R. R. et al. Towards identifying the active sites on RuO2(110) in catalyzing oxygen evolution. Energy Environ. Sci. 10, 2626–2637 (2017).

    Article  CAS  Google Scholar 

  48. Rao, R. R. et al. Operando identification of site-dependent water oxidation activity on ruthenium dioxide single-crystal surfaces. Nat. Catal. 3, 516–525 (2020).

    Article  CAS  Google Scholar 

  49. Stoerzinger, K. A. et al. Orientation-dependent oxygen evolution on RuO2 without lattice exchange. ACS Energy Lett. 2, 876–881 (2017).

    Article  CAS  Google Scholar 

  50. Rong, X., Parolin, J. & Kolpak, A. M. A fundamental relationship between reaction mechanism and stability in metal oxide catalysts for oxygen evolution. ACS Catal. 6, 1153–1158 (2016).

    Article  CAS  Google Scholar 

  51. Wu, Z.-Y. et al. Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat. Commun. 12, 2870 (2021).

    Article  CAS  Google Scholar 

  52. Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864–B871 (1964).

    Article  Google Scholar 

  53. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).

    Article  Google Scholar 

  54. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).

    Article  CAS  Google Scholar 

  55. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  58. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  60. 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  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Welch Foundation Research (grant no. C-2051-20200401), the David and Lucile Packard Foundation Packard Fellowship programme (grant no. 2020–71371) and the Roy E. Campbell Faculty Development Award. B.L. and G.W. gratefully acknowledge financial support for this research provided by the National Science Foundation (NSF) (grant no. DMR 1905572). S.Z. and S.-W.Y. gratefully acknowledge the financial support for this research provided by the NSF (grant no. CBET- 2004808). This work also used the computational resources provided by the University of Pittsburgh Center for Research Computing, and the resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by the Argonne National Laboratory under contract no. DE-AC02-06CH11357.

Author information

Author notes

  1. These authors contributed equally: Zhen-Yu Wu, Feng-Yang Chen, Boyang Li.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA

    Zhen-Yu Wu, Feng-Yang Chen, Peng Zhu & Haotian Wang

  2. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA, USA

    Boyang Li & Guofeng Wang

  3. Department of Chemistry, University of Virginia, Charlottesville, VA, USA

    Shen-Wei Yu, Zhouyang Yin & Sen Zhang

  4. Structural Biology Center, X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    Y. Zou Finfrock

  5. Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada

    Debora Motta Meira

  6. Department of Chemistry, University of Science and Technology of China, Hefei, China

    Qiang-Qiang Yan, Ming-Xi Chen, Tian-Wei Song & Hai-Wei Liang

  7. Department of Materials Science and NanoEngineering, Rice University, Houston, TX, USA

    Haotian Wang

  8. Department of Chemistry, Rice University, Houston, TX, USA

    Haotian Wang

Authors
  1. Zhen-Yu Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Feng-Yang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Boyang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shen-Wei Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Y. Zou Finfrock
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Debora Motta Meira
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qiang-Qiang Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Peng Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ming-Xi Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Tian-Wei Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Zhouyang Yin
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Hai-Wei Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Sen Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Guofeng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Haotian Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Z.-Y.W. and H.W. conceived the project. H.W., G.W. and S.Z. supervised the project. Z.-Y.W. developed the synthesis of catalysts. Z.-Y.W. and F.-Y.C. performed catalyst synthesis, catalytic tests and related data processing. Z.-Y.W., F.-Y.C., Y.Z.F., D.M.M. and P.Z. performed materials characterization. Q.-Q.Y., M.-X.C., T.-W.S. and H.-W.L. kindly helped with TEM and XAS data analysis. S.-W.Y., Z.Y. and S.Z. performed DEMS testing. B.L. and G.W. performed DFT simulation. Z.-Y.W., F.-Y.C., B.L., H.W. and G.W. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Sen Zhang, Guofeng Wang or Haotian Wang.

Ethics declarations

Competing interests

A patent application has been filed based on this study.

Peer review

Peer review information

Nature Materials thanks the anonymous reviewers 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.

Supplementary information

Supplementary Information

Supplementary Figs. 1–50, Tables 1–3, Notes 1 and 2 and References 1–30.

Rights and permissions

Springer Nature or its licensor 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

Wu, ZY., Chen, FY., Li, B. et al. Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis. Nat. Mater. 22, 100–108 (2023). https://doi.org/10.1038/s41563-022-01380-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-022-01380-5

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