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Pivotal role of reversible NiO6 geometric conversion in oxygen evolution

Nature volume 611, pages 702–708 (2022)Cite this article

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Abstract

Realizing an efficient electron transfer process in the oxygen evolution reaction by modifying the electronic states around the Fermi level is crucial in developing high-performing and robust electrocatalysts1,2,3. Typically, electron transfer proceeds solely through either a metal redox chemistry (an adsorbate evolution mechanism (AEM), with metal bands around the Fermi level) or an oxygen redox chemistry (a lattice oxygen oxidation mechanism (LOM), with oxygen bands around the Fermi level), without the concurrent occurrence of both metal and oxygen redox chemistries in the same electron transfer pathway1,2,3,4,5,6,7,8,9,10,11,12,13,14,15. Here we report an electron transfer mechanism that involves a switchable metal and oxygen redox chemistry in nickel-oxyhydroxide-based materials with light as the trigger. In contrast to the traditional AEM and LOM, the proposed light-triggered coupled oxygen evolution mechanism requires the unit cell to undergo reversible geometric conversion between octahedron (NiO6) and square planar (NiO4) to achieve electronic states (around the Fermi level) with alternative metal and oxygen characters throughout the oxygen evolution process. Utilizing this electron transfer pathway can bypass the potential limiting steps, that is, oxygen–oxygen bonding in AEM and deprotonation in LOM1,2,3,4,5,8. As a result, the electrocatalysts that operate through this route show superior activity compared with previously reported electrocatalysts. Thus, it is expected that the proposed light-triggered coupled oxygen evolution mechanism adds a layer of understanding to the oxygen evolution research scene.

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Fig. 1: Schematic illustration of OER routes.
Fig. 2: OER activities of traditional NiOOH and NR-NiOOH with and without light irradiation.
Fig. 3: Identification of redox activities for NR-NiOOH subjected to light irradiation.
Fig. 4: Proposed light-induced electron transfer process with switchable metal and oxygen redox centres for the OER.
Fig. 5: The origins of our proposed coupled evolution mechanism.

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The authors declare that all data supporting of the finding of this study are included within the paper and its Supplementary Information files and are available from the corresponding authors on request.

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Acknowledgements

We thank H. Wang and C. Wang for their help with figure design and A. Stefan for his advice on simulation. This work is financially supported by Singapore Ministry of Education (MOE) Tier 1 R284000226114 and MOE Tier 2 (MOE2018-T2-1-149), Agency for Science, Technology and Research (A*STAR) of Singapore. This research is also supported by A*STAR, grant number 152-70-00017, and computational resources were provided by National Supercomputing Centre Singapore (NSCC) and A*STAR Computational Resource Centre, Singapore (A*CRC). This project was partly supported by the Science and Engineering Research Council (SERC) of A*STAR of Singapore. This research is also supported by the Guangxi Bagui Scholar Foundation, Guilin Lijiang Scholar Foundation, Science and Technology Development Project of Guilin (20210216-1).

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Authors and Affiliations

  1. Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

    Xiaopeng Wang, Pengru Huang, Haoyin Zhong, Qing Wang, Wee Siang Vincent Lee & Junmin Xue

  2. Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research, Singapore, Singapore

    Shibo Xi & Armando Borgna

  3. Guangxi Collaborative Innovation Center of Structure and Property for New Energy, Guangxi Key Laboratory of Information Materials, School of Material Science and Engineering, Guilin University of Electronic Technology, Guilin, China

    Pengru Huang

  4. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Yonghua Du

  5. Institute of High Performance Computing, Agency for Science, Technology and Research, Singapore, Singapore

    Yong-Wei Zhang & Zhi Gen Yu

  6. School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Heilongjiang Sheng, Harbin, China

    Zhenbo Wang

  7. Department of Mechanical Engineering, National University of Singapore, Singapore, Singapore

    Hao Wang

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Contributions

X.W., S.X. and J.X. conceived the idea. X.W. and W.S.V.L. performed synthesis and electrochemical measurement of the samples. X.W., W.S.V.L., H.Z., Q.W., H.W. and Z.W. were responsible for the analysis of electrochemical results. S.X., Y.D. and A.B. were responsible for the XAFS characterization. Z.G.Y., P.H. and Y.-W.Z. carried out DFT simulations. J.X. is in charge of the overall project and preparation of the manuscript.

Corresponding authors

Correspondence to Shibo Xi, Hao Wang, Zhi Gen Yu, Wee Siang Vincent Lee or Junmin Xue.

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Wang, X., Xi, S., Huang, P. et al. Pivotal role of reversible NiO6 geometric conversion in oxygen evolution. Nature 611, 702–708 (2022). https://doi.org/10.1038/s41586-022-05296-7

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