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In situ Raman spectroscopy reveals the structure and dissociation of interfacial water

Nature volume 600, pages 81–85 (2021)Cite this article

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Abstract

Understanding the structure and dynamic process of water at the solid–liquid interface is an extremely important topic in surface science, energy science and catalysis1,2,3. As model catalysts, atomically flat single-crystal electrodes exhibit well-defined surface and electric field properties, and therefore may be used to elucidate the relationship between structure and electrocatalytic activity at the atomic level4,5. Hence, studying interfacial water behaviour on single-crystal surfaces provides a framework for understanding electrocatalysis6,7. However, interfacial water is notoriously difficult to probe owing to interference from bulk water and the complexity of interfacial environments8. Here, we use electrochemical, in situ Raman spectroscopic and computational techniques to investigate the interfacial water on atomically flat Pd single-crystal surfaces. Direct spectral evidence reveals that interfacial water consists of hydrogen-bonded and hydrated Na+ ion water. At hydrogen evolution reaction (HER) potentials, dynamic changes in the structure of interfacial water were observed from a random distribution to an ordered structure due to bias potential and Na+ ion cooperation. Structurally ordered interfacial water facilitated high-efficiency electron transfer across the interface, resulting in higher HER rates. The electrolytes and electrode surface effects on interfacial water were also probed and found to affect water structure. Therefore, through local cation tuning strategies, we anticipate that these results may be generalized to enable ordered interfacial water to improve electrocatalytic reaction rates.

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Fig. 1: Probing interfacial water on Pd(hkl) surfaces.
Fig. 2: Raman spectra of interfacial water.
Fig. 3: Water dissociation.
Fig. 4: HER profiles and Raman spectra of interfacial water.

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Data availability

The data generated or analysed during this study are included in this published article and its Supplementary information files. Source data are provided with this paper.

Code availability

The code that supports the findings of this research is available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2019YFA0705400, 2020YFB1505800, 2020YFB0704500 and 2019YFD0901100), the National Natural Science Foundation of China (21925404, 22021001, 21521004, 21775127, 21991151 and 21902137), the Shenzhen Science and Technology Research Grant (JCYJ20200109140416788) and ‘111’ Project (B17027). We thank Y. X. Chen, B. W. Mao, D. P. Zhan, Z. Wei and J. B. Le for fruitful discussions, and Q. Q. Zhao, M. F. Cao and Y. Hui for technical assistance.

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Author notes

  1. These authors contributed equally: Yao-Hui Wang, Shisheng Zheng

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, iChEM, College of Chemistry and Chemical Engineering, College of Energy, College of Materials, College of Physical Science and Technology, Xiamen University, Xiamen, China

    Yao-Hui Wang, Wei-Min Yang, Ru-Yu Zhou, Quan-Feng He, Petar Radjenovic, Jin-Chao Dong, Zhi-Lin Yang, Zhong-Qun Tian & Jian-Feng Li

  2. School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen, China

    Shisheng Zheng, Shunning Li, Jiaxin Zheng & Feng Pan

  3. Department of Physics, University of Liverpool, Liverpool, UK

    Gary Attard

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

    Zhong-Qun Tian & Jian-Feng Li

  5. College of Optical and Electronic Technology, China Jiliang University, Hangzhou, China

    Jian-Feng Li

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Contributions

Y.-H.W., S.Z., F.P. and J.-F.L. conceived the project; Y.-H.W., R.-Y.Z. and Q.-F.H. conducted the experiments; F.P., S.Z., S.L. and J.Z. performed the mechanism study and AIMD simulation; W.-M.Y. and Z.-L.Y. performed the 3D-FDTD simulation; Y.-H.W., S.Z., P.R., G.A., F.P., Z.-Q.T. and J.-F.L. wrote the paper. All authors participated in the analysis and discussion.

Corresponding authors

Correspondence to Feng Pan or Jian-Feng Li.

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Peer review information Nature thanks Angel Cuesta and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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This file includes Supplementary Notes, Figs. 1–21, Table 1 and Refs. 1–29.

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Wang, YH., Zheng, S., Yang, WM. et al. In situ Raman spectroscopy reveals the structure and dissociation of interfacial water. Nature 600, 81–85 (2021). https://doi.org/10.1038/s41586-021-04068-z

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