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Valence oscillation and dynamic active sites in monolayer NiCo hydroxides for water oxidation

Nature Catalysis volume 4, pages 1050–1058 (2021)Cite this article

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Abstract

Monolayer materials are endowed with an additional degree of freedom to modulate electronic structures and catalytic performances. Here, we report a direct synthesis of monolayer Ni(OH)2 on electrodes by in situ electrochemical conversion and a fundamental investigation of their catalytic activity. The monolayer structure greatly promotes hydrogen and oxygen release processes to produce dynamic active sites for the oxygen evolution reaction (OER) at a lower potential. Lattice doping with cobalt further tunes the electronic structure to reduce the overpotential. In situ experiments revealed Ni and Co valence state oscillation in NiCo hydroxides, which has been attributed to sequential dehydrogenation and deoxygenation processes, and fundamentally contributes to the dynamic generation of OER active sites. This study defines an in situ conversion process to yield monolayer layered double hydroxides (LDHs) and establishes a critical fundamental understanding of the origin of the active sites in monolayer LDHs for the OER.

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Fig. 1: Schematic of the conversion from molecular crystal to monolayer hydroxide and structure characterization.
Fig. 2: Relationship between the valence states of Ni and the dehydrogenation of mono- and multilayer Ni(OH)2.
Fig. 3: Production and detection of in situ generated oxygen vacancies by the release of oxygen atoms.
Fig. 4: Promotion of OER activity induced by in situ generated Ov.

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Data availability

The data supporting the findings of this study are available in the paper and its Supplementary Information. Additional data are available from the corresponding authors upon reasonable request.

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Acknowledgements

The work performed at Beihang University was supported by the National Natural Science Foundation of China (51532001, 11974037, U1930402 and 52002010), the Beijing Natural Science Foundation (2194077) and the National Postdoctoral Program for Innovative Talents (BX20180020). We thank S. Zhang of the Shanghai Institute of Applied Physics for providing the standard XAFS data, and J. Zhang and L. Zheng of Beijing Synchrotron Radiation Facility for help with the in situ XAFS tests. We acknowledge the support of the NSRL (Beamlines MCD-A and MCD-B, Soochow Beamline for Energy Materials) in the XAS experiments. The computer resources of Tianhe-2 and Beihang HPC are both acknowledged.

Author information

Author notes

  1. These authors contributed equally: Jianxin Kang, Xiaoyi Qiu, Qi Hu.

Authors and Affiliations

  1. School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Beihang University, Beijing, China

    Jianxin Kang, Xiaoyi Qiu & Lin Guo

  2. Beijing Computational Science Research Center, Beijing, China

    Qi Hu

  3. School of Physics, Beihang University, Beijing, China

    Qi Hu & Li-Min Liu

  4. Jiangsu Key Laboratory for Carbon-based Functional Materials and Devices, Institute of Functional Nano and Soft Materials, Soochow University, Suzhou, China

    Jun Zhong

  5. Center for High Pressure Science and Technology Advanced Research, Beijing, China

    Xiang Gao

  6. Key Laboratory of Polar Materials and Devices, East China Normal University, Shanghai, China

    Rong Huang

  7. Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA

    Chengzhang Wan & Xiangfeng Duan

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  1. Jianxin Kang
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Contributions

J.K., L.-M.L. and L.G. designed and directed the study. J.K. and X.Q. conceived and performed the fabrications. Q.H. and L.-M.L. performed the first-principles calculations and analysed the results. X.G. and R.H. performed the spherical aberration-corrected TEM analyses. J.K., X.Q. and J.Z. participated in the characterization studies. All authors contributed to the discussions. J.K., Q.H., J.Z., C.W., L.L., X.D. and L.G. analysed the data and wrote the manuscript. All authors reviewed the paper.

Corresponding authors

Correspondence to Li-Min Liu or Lin Guo.

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Peer review information Nature Catalysis thanks Hong-Jie Peng 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. 1–38, Discussions 1–3 and Table 1.

Supplementary Data

Optimized coordinates for the corresponding structures.

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Kang, J., Qiu, X., Hu, Q. et al. Valence oscillation and dynamic active sites in monolayer NiCo hydroxides for water oxidation. Nat Catal 4, 1050–1058 (2021). https://doi.org/10.1038/s41929-021-00715-w

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