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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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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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.
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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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Atomic coordinates of optimized computational models.
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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 7, 646–654 (2024). https://doi.org/10.1038/s41929-024-01148-x
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DOI: https://doi.org/10.1038/s41929-024-01148-x
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