Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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

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

Subjects

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.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

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.

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.

References

  1. Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).

    Article  Google Scholar 

  2. Mubeen, S. et al. An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. Nat. Nanotechnol. 8, 247–251 (2013).

    Article  ADS  CAS  Google Scholar 

  3. Guo, J. et al. Real-space imaging of interfacial water with submolecular resolution. Nat. Mater. 13, 184−189 (2014).

    Article  ADS  CAS  Google Scholar 

  4. Vidal-Iglesias, F. J., Solla-Gullon, J., Herrero, E., Aldaz, A. & Feliu, J. M. Pd adatom decorated (100) preferentially oriented Pt nanoparticles for formic acid electrooxidation. Angew. Chem. Int. Ed. 49, 6998–7001 (2010).

    Article  CAS  Google Scholar 

  5. Strmcnik, D. et al. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. Nat. Chem. 2, 880–885 (2010).

    Article  CAS  Google Scholar 

  6. Kendrick, E., Kendrick, J., Knight, K. S., Islam, M. S. & Slater, P. R. Cooperative mechanisms of fast-ion conduction in gallium-based oxides with tetrahedral moieties. Nat. Mater. 6, 871–875 (2007).

    Article  ADS  CAS  Google Scholar 

  7. Mesa, C. A. et al. Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT. Nat. Chem. 12, 82–89 (2020).

    Article  CAS  Google Scholar 

  8. Velasco-Velez, J. J. et al, The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy. Science 346, 831–834 (2014).

    Article  ADS  CAS  Google Scholar 

  9. Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012).

    Article  ADS  CAS  Google Scholar 

  10. Wang, X., Xu, C., Jaroniec, M., Zheng, Y. & Qiao, S. Z. Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions. Nat. Commun. 10, 4876 (2019).

    Article  ADS  Google Scholar 

  11. Ledezma-Yanez, I. et al. Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes. Nat. Energy 2, 17031 (2017).

    Article  ADS  CAS  Google Scholar 

  12. Guha, A., Narayanaru, S. & Narayanan, T. N. Tuning the hydrogen evolution reaction on metals by lithium salt. ACS Appl. Energy Mater. 1, 7116–7122 (2018).

    Article  CAS  Google Scholar 

  13. Guha, A., Kaley, N. M., Mondal, J. & Narayanan, T. N. Engineering the hydrogen evolution reaction of transition metals: effect of Li ions. J. Mater. Chem. A 8, 15795–15808 (2020).

    Article  CAS  Google Scholar 

  14. Ataka, K., Yotsuyanagi, T. & Osawa, M. Potential-dependent reorientation of water molecules at an electrode/electrolyte interface studied by surface-enhanced infrared absorption spectroscopy. J. Phys. Chem. 100, 10664–10672, (1996).

    Article  CAS  Google Scholar 

  15. Yamakata, A. & Osawa, M. Destruction of the hydration shell around tetraalkylammonium ions at the electrochemical interface. J. Am. Chem. Soc. 131, 6892–6893, (2009).

    Article  CAS  Google Scholar 

  16. Tong, Y., Lapointe, F., Thamer, M., Wolf, M. & Campen, R. K. Hydrophobic water probed experimentally at the gold electrode/aqueous interface. Angew. Chem. Int. Ed. 56, 4211–4214 (2017).

    Article  CAS  Google Scholar 

  17. Liu, W. T. & Shen, Y. R. In situ sum-frequency vibrational spectroscopy of electrochemical interfaces with surface plasmon resonance. Proc. Natl Acad. Sci. USA 111, 1293–1297 (2014).

    Article  ADS  CAS  Google Scholar 

  18. Li, J. F. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464, 392–395 (2010).

    Article  ADS  CAS  Google Scholar 

  19. Dong, J. C. et al. In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces. Nat. Energy 4, 60–67 (2019).

    Article  ADS  CAS  Google Scholar 

  20. Davis, J. G., Gierszal, K. P., Wang, P. & Ben-Amotz, D. Water structural transformation at molecular hydrophobic interfaces. Nature 491, 582–585 (2012).

    Article  ADS  CAS  Google Scholar 

  21. Chen, Y. X., Zou, S. Z., Huang, K. Q. & Tian, Z. Q. SERS studies of electrode/electrolyte interfacial water part II–librations of water correlated to hydrogen evolution reaction. J. Raman Spectrosc. 29, 749–756 (1998).

    Article  ADS  CAS  Google Scholar 

  22. Toney, M. F. et al. Voltage-dependent ordering of water molecules at an electrode-electrolyte interface. Nature 368, 444–446 (1994).

    Article  ADS  CAS  Google Scholar 

  23. Senior, W. A. & Thompson, W. K. Assignment of the infra-red and Raman bands of liquid water. Nature 205, 170 (1965).

    Article  ADS  CAS  Google Scholar 

  24. Chen, H. C. et al. Active and stable liquid water innovatively prepared using resonantly illuminated gold nanoparticles. ACS Nano 8, 2704–2713 (2014).

    Article  CAS  Google Scholar 

  25. Scatena, L. F., Brown, M. G. & Richmond, G. L. Water at hydrophobic surfaces: weak hydrogen bonding and strong orientation effects. Science 292, 908–912 (2001).

    Article  ADS  CAS  Google Scholar 

  26. Lambert, D. K. Vibrational Stark effect of adsorbates at electrochemical interfaces. Electrochim. Acta 41, 623–630 (1996).

    Article  CAS  Google Scholar 

  27. Li, J. F. et al. SERS and DFT study of water on metal cathodes of silver, gold and platinum nanoparticles. Phys. Chem. Chem. Phys. 12, 2493–2502 (2010).

    Article  CAS  Google Scholar 

  28. Subbaraman, R. et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2-Pt interfaces. Science 334, 1256–1260 (2011).

    Article  ADS  CAS  Google Scholar 

  29. Kibler, L. A. Hydrogen electrocatalysis. ChemPhysChem 7, 985–991 (2006).

    Article  CAS  Google Scholar 

  30. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  ADS  CAS  Google Scholar 

  31. Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).

    Article  ADS  Google Scholar 

  32. Tonigold, K. & Gross, A. Dispersive interactions in water bilayers at metallic surfaces: a comparison of the PBE and RPBE functional including semiempirical dispersion corrections. J. Comput. Chem. 33, 695–701 (2012).

    Article  CAS  Google Scholar 

  33. Sakong, S., Forster-Tonigold, K. & Gross, A. The structure of water at a Pt(111) electrode and the potential of zero charge studied from first principles. J. Chem. Phys. 144, 194701 (2016).

    Article  ADS  Google Scholar 

  34. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    Article  ADS  Google Scholar 

Download references

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.

Author information

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

Authors
  1. Yao-Hui Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shisheng Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wei-Min Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ru-Yu Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Quan-Feng He
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Petar Radjenovic
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jin-Chao Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Shunning Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Jiaxin Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Zhi-Lin Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Gary Attard
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Feng Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Zhong-Qun Tian
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Jian-Feng Li
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Source data

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41586-021-04068-z

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing