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Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid

Nature Catalysis volume 5, pages 109–118 (2022)Cite this article

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Abstract

Active and stable electrocatalysts for the oxygen evolution reaction are required to produce hydrogen from water using renewable electricity. Here we report that incorporating Mn into the spinel lattice of Co3O4 can extend the catalyst lifetime in acid by two orders of magnitude while maintaining the activity. The activation barrier of the obtained spinel Co2MnO4 is comparable to that of state-of-the-art iridium oxides, most probably due to the ideal binding energies of the oxygen evolution reaction intermediates, as shown using density functional theory calculations. The calculations also show that the thermodynamic landscape of Co2MnO4 suppresses dissolution, which results in a lifetime of over 2 months (1,500 hours) at 200 mA cm−2geo at pH 1. As the lifetimes of other 3d metal oxygen evolution catalysts are in the order of days and weeks, despite current densities being lower by an order of magnitude, our results are an important step towards the realization of noble-metal-free water electrolysers.

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Fig. 1: Characterization of Co2MnO4 before and after electrolysis.
Fig. 2: OER activity of Co2MnO4 at 25 °C.
Fig. 3: OER activities at elevated temperature.
Fig. 4: Long-term stability of Co2MnO4 during the OER in acid.
Fig. 5: Mechanistic investigation and activity predictions.
Fig. 6: Theoretical stability investigations.

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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. The structural parameters derived from the Rietveld refinement are given in Supplementary Data 2–4 for Co2MnO4 before electrolysis and after electrolysis for 4 h and 23 h, respectively. The structures are also available from the Cambridge Crystal Structure Data Centre (https://www.ccdc.cam.ac.uk/) with the deposition codes 2098166, 2098164 and 2098165 for Co2MnO4 before the electrolysis and after the electrolysis at 4 and 23 h, respectively.

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Acknowledgements

We thank T. Kikitsu and K. Takahashi at RIKEN for assistance with TEM and ICP-MS measurements and analysis. The synchrotron radiation experiments were performed at the BL14B2 (XAFS) and BL44B2 (SR-PXRD) of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal no. 2021A2013) and RIKEN (proposal no. 20210064), respectively. The XAFS spectrum of LiMn2O4 was utilized by the SPring-8 BL14B2 XAFS database. This work was supported by the New Energy and Industrial Technology Development Organization (NEDO) and JSPS Grant-in-Aid for Scientific Research (no. 18H02070). H.H. also thanks the National Key R&D Program of China (no. 2017YFA0204804) and the National Natural Science Foundation of China (no. 21761142018). J.X. acknowledges the financial support from the National Key R&D Program of China (No. 2021YFA1500702), the DNL Cooperation Fund, CAS (no. DNL202003), the National Natural Science Foundation of China (22172156, 91845103, 91945302 and 21802124), the Strategic Priority Research Program of Chinese Academy of Sciences (no. XDB36030200), the funding support by the LiaoNing Revitalization Talents Program (XLYC1907099) and the State Key Laboratory of Catalysis in DICP (no. N-19-13).

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Author notes

  1. These authors contributed equally: Ailong Li, Shuang Kong and Chenxi Guo.

Authors and Affiliations

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

    Ailong Li, Shuang Kong, Hideshi Ooka, Hongxian Han & Ryuhei Nakamura

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

    Chenxi Guo, Hongxian Han & Jianping Xiao

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

    Kiyohiro Adachi & Daisuke Hashizume

  4. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Qike Jiang, Hongxian Han & Jianping Xiao

  5. School of Future Technology, University of Chinese Academy of Sciences, Beijing, China

    Hongxian Han

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

    Ryuhei Nakamura

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Contributions

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

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Correspondence to Jianping Xiao or Ryuhei Nakamura.

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Nature Catalysis thanks Jongwoo Lim, Nan Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–59, Tables 1–24, Notes 1–3 and references.

Supplementary Video 1

Bubble generation from a Co2MnO4 catalyst deposited on an FTO substrate at room temperature (25 °C) at current densities of 20 mA cm−2geo, 50 mA cm−2geo, 100 mA cm−2geo, 200 mA cm−2geo, 500 mA cm−2geo and 1,000 mA cm−2geo, respectively.

Supplementary Data 1

The atomic coordinates of the computational models.

Supplementary Data 2

Crystallographic data of Co2MnO4 before electrolysis derived from Rietveld refinement.

Supplementary Data 3

Crystallographic data of Co2MnO4 after electrolysis at 100 mA cm−2geo (pH 1 H2SO4, 25 °C) for 4 h derived from Rietveld refinement.

Supplementary Data 4

Crystallographic data of Co2MnO4 after electrolysis at 100 mA cm−2geo (pH 1 H2SO4, 25 °C) for 23 h derived from Rietveld refinement.

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Li, A., Kong, S., Guo, C. et al. Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid. Nat Catal 5, 109–118 (2022). https://doi.org/10.1038/s41929-021-00732-9

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