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Chemistry governs water organization at a graphene electrode

Nature volume 615, pages E1–E2 (2023)Cite this article

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The Original Article was published on 02 June 2021

arising from A. Montenegro et al. Nature https://doi.org/10.1038/s41586-021-03504-4 (2021)

Knowledge of the molecular structure and orientation of interfacial water molecules next to a potentiostatically controlled electrode surface is of fundamental and technological importance and an enigma in surface science1,2,3. Montenegro et al.4 investigated the interfacial structure of heavy water (D2O) on a graphene electrode surface using homodyne-detected sum-frequency generation (SFG) spectroscopy and inferred an asymmetric response of the interfacial water to the applied electric field on the basis of the appearance of a high-frequency OD stretch peak at 2,700 cm−1 for potentials below −1.0 V. However, our heterodyne-detected SFG (HD-SFG) spectra show that the sign of the peak is negative, in contrast to the fit proposed by Montenegro et al.4.The negative sign indicates that the peak does not arise from the interfacial water molecules but rather from OD groups on the underlying substrate of the graphene electrode, putting their conclusion into question.

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Fig. 1: OH stretching spectra at the CaF2-supported electrified graphene–water interface measured by HD-SFG.

Data availability

The data that support the findings shown in Fig. 1 and Supplementary Figs. 1–9 are available from the corresponding authors upon reasonable request.

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Author notes

  1. These authors contributed equally: Yongkang Wang, Takakazu Seki

Authors and Affiliations

  1. School of Mechanical Engineering, Southeast University, Nanjing, China

    Yongkang Wang & Yunfei Chen

  2. Max Planck Institute for Polymer Research, Mainz, Germany

    Yongkang Wang, Takakazu Seki, Xiaoqing Yu, Chun-Chieh Yu, Kuo-Yang Chiang, Katrin F. Domke, Johannes Hunger, Yuki Nagata & Mischa Bonn

  3. Faculty of Chemistry, University Duisburg-Essen, Essen, Germany

    Katrin F. Domke

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  1. Yongkang Wang
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Contributions

Y.W. prepared the sample and characterized the sample with Raman and electrochemical measurements. Y.W. and T.S. performed the HD-SFG measurement and data analysis. Y.W., T.S., Y.C., Y.N., and M.B. wrote and modified the manuscript. All authors discussed the results.

Corresponding authors

Correspondence to Yunfei Chen, Yuki Nagata or Mischa Bonn.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

This file contains more details about the preparation and characterization of the samples, HD-SFG and Raman measurements, and data analysis. It includes sections 1–8, Supplementary Figs. 1–9 and additional references.

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Wang, Y., Seki, T., Yu, X. et al. Chemistry governs water organization at a graphene electrode. Nature 615, E1–E2 (2023). https://doi.org/10.1038/s41586-022-05669-y

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