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Acid-stable manganese oxides for proton exchange membrane water electrolysis

Nature Catalysis volume 7, pages 252–261 (2024)Cite this article

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Abstract

Earth-abundant, acid-stable catalysts for the oxygen evolution reaction are essential for terawatt-scale hydrogen production using proton exchange membrane (PEM) electrolysers. Here we report that optimizing the lattice oxygen structure of manganese oxide allows it to sustain the oxygen evolution reaction for over one month at 1,000 mA cm−2 in 1 M H2SO4. The lifetime enhancement was achieved by substituting pyramidal oxygen with planar oxygen, which has a stronger Mn–O bond and thus suppresses the dissolution of manganese ions. Calculations show that the lattice oxygen dissolution is the bottleneck of deactivation, and this process is less favourable by over 0.2 eV on planar oxygen compared with pyramidal oxygen. Our material shows excellent performance even in a PEM electrolyser, reaching 2,000 mA cm−2 at 2 V with durability exceeding 1,000 h at 200 mA cm−2. This study expands the potential of Earth-abundant catalysts for PEM electrolysis, which may mitigate the reliance on iridium.

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Fig. 1: Characterization of synthesized γ-MnO2 materials.
Fig. 2: Spectroelectrochemical measurements of the four γ-MnO2 catalysts.
Fig. 3: Long-term OER stability of γ-MnO2 in acidic electrolyte and theoretical analysis.
Fig. 4: Performance of γ-MnO2 for PEM electrolysis at 80 °C and theoretical analysis.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon request. The atomic coordinates of the computational models are given in Supplementary Data 1.

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Acknowledgements

The synchrotron radiation experiments were performed at BL14B2 (XAFS) and BL44B2 (SR-PXRD) of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal numbers 2021A1664, 2022B1667 and 2022A1045) and RIKEN (proposal numbers 20210064, 20220057 and 20230043). We thank H. Ofuchi (JASRI) for the XAFS experiments, and K. Kato (RIKEN) and K. Shigeta (Nippon Gijutsu Center) for the SR-PXRD and total scattering experiments. We thank T. Wakashima (RIKEN) for his assistance with creating the graphical abstract. This work was partially supported by the New Energy and Industrial Technology Development Organization (NEDO, JPNP14021). R.N. acknowledges JSPS Grant-in-Aid for Scientific Research (22H00339). J.X. acknowledges financial supports from the National Key Research and Development Program of China (2021YFA1500702), the National Natural Science Foundation of China (22172156 and 22321002), the AI S&T Program of Yulin Branch, Dalian National Laboratory for Clean Energy, CAS (DNL-YLA202205, J.X.) and DNL Cooperation Fund, CAS (DNL202003).

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Author notes

  1. These authors contributed equally: Shuang Kong, Ailong Li, Jun Long.

Authors and Affiliations

  1. Biofunctional Catalyst Research Team, RIKEN Center for Sustainable Resource Science (CSRS), Wako, Japan

    Shuang Kong, Ailong Li, Kazuna Fushimi, Hideshi Ooka & Ryuhei Nakamura

  2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Jun Long & Jianping Xiao

  3. Materials Characterization Support Team, RIKEN Center for Emergent Matter Science (CEMS), Wako, Japan

    Kiyohiro Adachi & Daisuke Hashizume

  4. Instrumentation and Service Center for Physical Sciences, Westlake University, Hangzhou, China

    Qike Jiang

  5. Earth-Life Science Institute (ELSI), Tokyo Institute of Technology, Tokyo, Japan

    Ryuhei Nakamura

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  1. Shuang Kong
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Contributions

S.K., A.L. and R.N. conceived and designed the experiments. S.K., A.L., K.A., K.F. and Q.J. performed the experiments. J.L. and J.X. performed the DFT calculations. S.K., A.L., H.O., K.A., D.H. and R.N. analysed the data. S.K., A.L., J.L., H.O., J.X. and R.N. co-wrote the paper. All the authors discussed the results and reviewed the manuscript.

Corresponding authors

Correspondence to Ailong Li, Jianping Xiao or Ryuhei Nakamura.

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Nature Catalysis thanks Bin Dong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–50, Tables 1–13, Notes 1–4 and References.

Supplementary Data 1

The atomic coordinates of the computational models.

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Kong, S., Li, A., Long, J. et al. Acid-stable manganese oxides for proton exchange membrane water electrolysis. Nat Catal 7, 252–261 (2024). https://doi.org/10.1038/s41929-023-01091-3

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