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Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface

Nature Energy volume 8, pages 859–869 (2023)Cite this article

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Abstract

Rational construction of the electrode–solution interface where electrochemical processes occur is of paramount importance in electrochemistry. Efforts to gain better control and understanding of the interface have been hindered by lack of probing methods. Here we show that the hydrogen evolution and oxidation reactions (HER/HOR) catalysed by platinum in base can be promoted by introduction of N-methylimidazoles at the platinum–water interface. In situ spectroscopic characterization together with simulations indicate that the N-methylimidazoles facilitate diffusion of hydroxides across the interface by holding the second layer of water close to platinum surfaces, thereby promoting the HER/HOR. We thus propose that the HER/HOR kinetics of platinum in acid and base is governed by diffusion of protons and hydroxides, respectively, through the hydrogen-bond network of interfacial water by the Grotthuss mechanism. Moreover, we demonstrate a 40% performance improvement of an anion exchange membrane electrolyser by adding 1,2-dimethylimidazole into the alkali fed into its platinum cathode.

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Fig. 1: Structurally dependent promotion effects of organic compounds on the HOR/HER of Pt.
Fig. 2: N-methylimidazoles promote the HOR/HER of Pt through the N3···H2O bonding.
Fig. 3: In situ probe of interfacial water and N-dimethylimidazoles.
Fig. 4: The Volmer step at the H2O–Pt(100) interface with/without Me-N1C2.
Fig. 5: Proposed mechanisms for the Volmer process on Pt surfaces.
Fig. 6: Me-N1C2 improves the AEMEL performance.

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Data availability

The data supporting the findings of this study are available within this article and its Supplementary Information. Additional data are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Office of Naval Research (ONR) grant N000141712608 (Q.J.). This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory Contract DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium Grant DE-SC0012335. W.A.G. acknowledges support by the Liquid Sunlight Alliance, which is supported by the US DOE, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under award number DE-SC0021266. This work used the Extreme Science and Engineering Discovery Environment (XSEDE) for AIMD simulation, which is supported by the NSF grant number ACI-1548562. S.K. acknowledges support from the Resnick Sustainability Institute at Caltech.

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Author notes

  1. Qingying Jia

    Present address: Plug Power Inc, Concord, MA, USA

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Northeastern University, Boston, MA, USA

    Qiang Sun, Jason J. Guo, Nathalie Myrthil, Steven A. Lopez, Ian Kendrick, Sanjeev Mukerjee & Qingying Jia

  2. Center for Clean Hydrogen, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Nicholas J. Oliveira & Yushan Yan

  3. Liquid Sunlight Alliance (LiSA) and Materials and Process Simulation Center (MSC), California Institute of Technology, Pasadena, CA, USA

    Soonho Kwon & William A. Goddard III

  4. Center for Drug Discovery and Departments of Pharmaceutical Sciences and Chemistry and Chemical Biology, Northeastern University, Boston, MA, USA

    Sergiy Tyukhtenko

  5. Barnett Institute for Chemical and Biological Analysis, Northeastern University, Boston, MA, USA

    Jason J. Guo

  6. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Lu Ma & Steven N. Ehrlich

  7. School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China

    Jingkun Li

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Contributions

Q.J. conceived the project, designed the experiments and proposed the HER/HOR mechanism. Q.S. conducted the electrochemical experiments and the data analysis in S.M.’s lab partly under his supervision. S.T. and J.J.G. conducted the NMR experiments and analysed the data. Q.S. helped to prepare the NMR samples. S.K. and W.A.G. planned the AIMD calculations. N.M. and S.A.L. performed the DFT calculations and contributed to the writing of the DFT computational results. Y.Y. and N.J.O. conducted the in situ ATR-SEIRAS and data analysis. Y.Y. and N.J.O. repeated electrochemical RDE experiments. Q.S., L.M. and S.N.E. conducted the XAS experiments, and Q.J. did the data analysis. J.L. conducted the in situ surface-enhanced Raman and data analysis. Q.S. and I.K. conducted the AEMEL testing and analysed the data. Q.J. supervised the project and data analysis. Q.J., Y.Y., W.A.G., Q.S., N.J.O. and S.K. wrote the paper and prepared the figures.

Corresponding authors

Correspondence to Jingkun Li, William A. Goddard III, Yushan Yan or Qingying Jia.

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The authors declare no competing interests.

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Nature Energy thanks Batyr Garlyyev, Zhenhua Zeng 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. 1–15, Tables 1–5, Notes 1–3 and References.

Supplementary Data 1

Raw data for the 60H2O-Pt configuration.

Supplementary Data 2

Raw data for the parallel Me-N1C2-57H2O-Pt configuration.

Supplementary Data 3

The deposition history of Gaussian potential with Me-N1C2.

Supplementary Data 4

The deposition history of Gaussian potential without Me-N1C2.

Supplementary Data 5

The time evolution of CV and potential energy landscape as a function of CV with Me-N1C2.

Supplementary Data 6

The time evolution of CV and potential energy landscape as a function of CV without Me-N1C2.

Supplementary Data 7

Raw data for Supplementary Fig. 15.

Supplementary Video 1

Video shows the movement of the hydroxide generated from HER absent of Me-N1C2.

Supplementary Video 2

Video shows the movement of the hydroxide generated from HER with the presence of Me-N1C2.

Source data

Source Data Fig. 1

Input data in Excel for Fig. 1.

Source Data Fig. 2

Input data in Excel for Fig. 2.

Source Data Fig. 3

Input data in Excel for Fig. 3.

Source Data Fig. 4

Input data in Excel for Fig. 4.

Source Data Fig. 6

Input data in Excel for Fig. 6.

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Sun, Q., Oliveira, N.J., Kwon, S. et al. Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface. Nat Energy 8, 859–869 (2023). https://doi.org/10.1038/s41560-023-01302-y

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