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Redirecting dynamic surface restructuring of a layered transition metal oxide catalyst for superior water oxidation

Nature Catalysis volume 4, pages 212–222 (2021)Cite this article

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Abstract

Rationally manipulating the in situ formed catalytically active surface of catalysts remains a tremendous challenge for a highly efficient water electrolysis. Here we present a cationic redox-tuning method to modulate in situ catalyst leaching and to redirect the dynamic surface restructuring of layered LiCoO2–xClx (x = 0, 0.1 or 0.2), for the electrochemical oxygen evolution reaction (OER). Chlorine doping lowered the potential to trigger in situ cobalt oxidation and lithium leaching, which induced the surface of LiCoO1.8Cl0.2 to transform into a self-terminated amorphous (oxy)hydroxide phase during the OER. In contrast, Cl-free LiCoO2 required higher electrochemical potentials to initiate the in situ surface reconstruction to spinel-type Li1±xCo2O4 and longer cycles to stabilize it. Surface-restructured LiCoO1.8Cl0.2 outperformed many state-of-the-art OER catalysts and demonstrated remarkable stability. This work makes a stride in modulating surface restructuring and in designing superior OER electrocatalysts via manipulating the in situ catalyst leaching.

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Fig. 1: Structural and compositional characterizations.
Fig. 2: Electronic configuration.
Fig. 3: OER performance in 1 M KOH.
Fig. 4: Operando XAFS test.
Fig. 5: Postmortem characterization of cycled LiCoO1.8Cl0.2.
Fig. 6: Theoretical understanding of Cl doping in redirecting surface restructuring.

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Data availability

Most data supporting the findings of this study are available from the main text of the article and its Supplementary Information. More data can be obtained from the corresponding authors upon reasonable request.

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Acknowledgements

We acknowledge the National Research Foundation of Korea (NRF) grants funded by the Korean government (MSIT) (no. NRF-2018M1A2A2063868, no. NRF-2019R1A4A1025848, no. NRF-2019M3E6A1065102, no. 2015M3D1A1070639, and no. NRF-2018R1C1B6006854). J. Lim also acknowledges support from the Samsung Science and Technology Foundation under project no. SRFC-MA2002-04. We express thanks to the staff and crew of the Seoul National University Electron Microscopy Facility (NCIRF), Research Institute of Advanced Materials (RIAM), the Institute of Applied Physics of Seoul National University and the Seoul National University Co-operative Flexible Transformative (SOFT) Foundry. J.W. gratefully acknowledges the SNU Science Fellowship (NRF-2019R1A6A1A10073437) funded by the Korean government (MSIT).

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Authors and Affiliations

  1. Department of Chemistry, College of Science, Seoul National University, Seoul, Republic of Korea

    Jian Wang, Subin Choi, Jeongwoo Han, Sugeun Jo, Juwon Kim, Hwiho Kim & Jongwoo Lim

  2. Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon, Republic of Korea

    Se-Jun Kim & Hyungjun Kim

  3. Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Hong Kong, China

    Jiapeng Liu & Francesco Ciucci

  4. College of Materials Science and Engineering, Hunan University, Changsha, China

    Yang Gao

  5. Graduate School of Energy Science and Technology (GEST), Chungnam National University, Daejeon, Republic of Korea

    Hyeyoung Shin

  6. Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Hong Kong, China

    Francesco Ciucci

  7. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Qingtian Li & Wanli Yang

  8. Guangdong Provincial Key Lab of Nano-Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, China

    Xia Long & Shihe Yang

  9. National Center for Inter-University Research Facilities, Seoul National University, Seoul, Republic of Korea

    Sung-Pyo Cho

  10. Beamline Research Division, Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang, Republic of Korea

    Keun Hwa Chae & Min Gyu Kim

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Contributions

J.W. contributed to the experimental planning, sample preparation, electrochemical experiments, synchrotron-based experiments, data analysis and manuscript preparation. S.-J.K., Y.G., H.S. and Hyungjun Kim conducted the DFT calculations and contributed to manuscript preparation. S.C., K.H.C., J.K. and M.G.K. supported the operando XAFS and ex situ sXAS experiments. J.H. and S.-P.C. conducted the TEM/STEM analysis. S.J. and Hwiho Kim contributed to the ICP-MS and XPS tests. Q.L. and W.Y. performed the RIXS experiments. J. Liu., F.C., X.L. and S.Y. assisted with the sample preparation, electrochemical test, data acquisition and analysis. J. Lim. supervised the project and contributed to the experimental planning, data analysis and manuscript preparation. All authors reviewed and commented on the manuscript before publication.

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Correspondence to Jian Wang, Shihe Yang, Hyungjun Kim or Jongwoo Lim.

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Peer review information Nature Catalysis thanks Marcel Risch, Kirsten Winther 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. 1–40, Tables 1–11 and Notes 1–7.

Supplementary Data

DFT-optimized structures.

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Wang, J., Kim, SJ., Liu, J. et al. Redirecting dynamic surface restructuring of a layered transition metal oxide catalyst for superior water oxidation. Nat Catal 4, 212–222 (2021). https://doi.org/10.1038/s41929-021-00578-1

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