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Visualizing the structural evolution of individual active sites in MoS2 during electrocatalytic hydrogen evolution reaction

Nature Catalysis (2024)Cite this article

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Abstract

Understanding the structural evolution of individual active sites during a reaction is a long-standing target in surface science and catalysis. It is still challenging to precisely characterize in situ the intrinsic nature and evolution of the active site because the active site is too small for characterization techniques to decipher the local properties. Here we used electrochemical tip-enhanced Raman spectroscopy to monitor the geometric and electronic evolution of individual active sites of MoS2 during the hydrogen evolution reaction. Reconstruction regions of 40 nm with varied lattice and electron density from the edge to the nearby basal plane were observed during the hydrogen evolution reaction. We further revealed the progressive generation of active sites during the activation process. The synergistic reconstruction around edge due to the lattice deformation reduces the activation energy barriers and promotes the electrocatalytic reaction. These discoveries offer insights into our understanding of the active site and its dynamics during electrocatalysis.

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Fig. 1: EC-TERS study of active and inactive sites in ultrathin MoS2 during the HER.
Fig. 2: EC-TERS spectral evolution of MoS2 during the HER.
Fig. 3: Lattice reconstruction and electronic transition regions induced by the edge.
Fig. 4: EC-TERS study of MoS2 during electrochemical activation.
Fig. 5: Structural evolution of the edge in atomically thin MoS2 in different states.

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Data availability

Data that support the findings of this study are available within the paper, the Supplementary Information and the Source data files. Additional data are available from the authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (NSFC) (grant numbers 22021001, 22227802, 21790354, 11874350, 92061118, 22372141 and 62374158), the National Key R&D Program of China (grant number 2023YFA1407000), the Strategic Priority Research Program of CAS (grant number XDB0460000), the Fundamental Research Funds for the Central Universities (grant number 20720220016) and the CAS Key Research Program of Frontier Sciences (grant numbers ZDBS-LY-SLH004 and XDPB22). We thank X. Yang for his assistance with theoretical discussion.

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Author notes

  1. These authors contributed equally: Teng-Xiang Huang, Xin Cong.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), MOE Key Laboratory of Spectrochemical Analysis & Instrumentation, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Teng-Xiang Huang, Si-Si Wu, Yi-Fan Bao, Mao-Feng Cao, Liwen Wu, Xiang Wang & Bin Ren

  2. State Key Laboratory of Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, Beijing, China

    Xin Cong, Jiang-Bin Wu, Miao-Ling Lin & Ping-Heng Tan

  3. Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, China

    Xiang Wang & Bin Ren

  4. Center of Materials Science and Optoelectronics Engineering & CAS Center of Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing, China

    Ping-Heng Tan

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Contributions

T.-X.H., X.W. and B.R. conceived the project. T.-X.H., S.-S.W. and Y.-F.B. performed the experiments. M.-F.C. fabricated the SiO2-coated gold tip. X.C., J.-B.W., M.-L.L. and P.-H.T. performed the DFT calculations. L.W. helped with the experiments. T.-X.H., X.C., X.W. and B.R. wrote the manuscript. All authors participated in the analysis and discussion.

Corresponding authors

Correspondence to Xiang Wang, Ping-Heng Tan or Bin Ren.

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Nature Catalysis thanks Patrick Unwin, Katrin F. Domke 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. 1–20, Notes 1–5 and Tables 1 and 2.

Supplementary Data 1

Atomic coordinates of optimized computational models.

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Source Data Fig. 1

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Source Data Fig. 2

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Source Data Fig. 3

Source data used to plot Fig. 3

Source Data Fig. 4

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Huang, TX., Cong, X., Wu, SS. et al. Visualizing the structural evolution of individual active sites in MoS2 during electrocatalytic hydrogen evolution reaction. Nat Catal (2024). https://doi.org/10.1038/s41929-024-01148-x

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