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Solutal Marangoni effect determines bubble dynamics during electrocatalytic hydrogen evolution

Nature Chemistry volume 15, pages 1532–1540 (2023)Cite this article

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Abstract

Understanding and manipulating gas bubble evolution during electrochemical water splitting is a crucial strategy for optimizing the electrode/electrolyte/gas bubble interface. Here gas bubble dynamics are investigated during the hydrogen evolution reaction on a well-defined platinum microelectrode by varying the electrolyte composition. We find that the microbubble coalescence efficiency follows the Hofmeister series of anions in the electrolyte. This dependency yields very different types of H2 gas bubble evolution in different electrolytes, ranging from periodic detachment of a single H2 gas bubble in sulfuric acid to aperiodic detachment of small H2 gas bubbles in perchloric acid. Our results indicate that the solutal Marangoni convection, induced by the anion concentration gradient developing during the reaction, plays a critical role at practical current density conditions. The resulting Marangoni force on the H2 gas bubble and the bubble departure diameter therefore depend on how surface tension varies with concentration for different electrolytes. This insight provides new avenues for controlling bubble dynamics during electrochemical gas bubble formation.

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Fig. 1: Anion effects on HER current oscillation and H2 gas bubble evolution.
Fig. 2: Anion effects during single H2 gas bubble growth.
Fig. 3: Anion effects on single H2 gas bubble detachment.
Fig. 4: Schematic illustration of the thermal and solutal Marangoni effects on H2 gas bubble evolution.
Fig. 5: HER current oscillations in mixed electrolytes of H2SO4 and HCl.
Fig. 6: Surface tension change ratio due to the temperature and ion concentration (σT = ∂σ/∂T and σC = ∂σ/∂C) as function of the applied potential.

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Data availability

All relevant data generated and analysed during this study are included in this article and its Supplementary Information. Data for the main figures are available in Zenodo (https://doi.org/10.5281/zenodo.7867261).

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Acknowledgements

This research received funding from the Dutch Research Council (NWO) in the framework of the ENW PPP Fund for the top sectors, from the Ministry of Economic Affairs in the framework of the PPS-toeslagregeling (grant number 741.019.201) and from the Advanced Research Center Chemical Building Blocks Consortium (ARC CBBC), under the project of New Chemistry for a Sustainable Future (project number 2021.038.C.UT.14). Additionally, the research is funded by Shell, Nobian and Nouryon. S.P. acknowledges the support by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2021R1A6A3A14039678). D.K., D.L. and M.T.M.K. received funding from the European Research Council (ERC) (BU-PACT grant agreement number 950111, ERC Advanced grant number 740479-DDD and ERC Advanced Grant ‘FRUMKIN’ number 101019998, respectively). We thank A. Bashkatov for insightful discussions on the subject.

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Authors and Affiliations

  1. Leiden Institute of Chemistry, Leiden University, Leiden, the Netherlands

    Sunghak Park, Onno van der Heijden & Marc T. M. Koper

  2. Physics of Fluids Group, Max Planck Center Twente for Complex Fluid Dynamics, Faculty of Science and Technology, University of Twente, Enschede, the Netherlands

    Luhao Liu, Çayan Demirkır, Detlef Lohse & Dominik Krug

  3. Max Planck Institute for Dynamics and Self-Organization, Göttingen, Germany

    Detlef Lohse

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Contributions

S.P. and M.T.M.K. conceived the project. S.P., D.K. and M.T.M.K. designed the experiments. S.P. and O.v.d.H. carried out electrochemical characterization. S.P., L.L., Ç.D., D.L. and D.K. carried out bubble dynamics analysis. All authors read and commented on the manuscript. All authors approved the final version of the manuscript.

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Correspondence to Dominik Krug or Marc T. M. Koper.

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Supplementary information

Supplementary Information

Supplementary Notes 1 and 2, Figs. 1–17, Table 1 and References.

Supplementary Video 1

H2 gas bubble evolution in 1 M H2SO4 at −0.16 VRHE.

Supplementary Video 2

H2 gas bubble evolution in 1 M HCl at −0.16 VRHE.

Supplementary Video 3

H2 gas bubble evolution in 1 M HNO3 at −0.16 VRHE.

Supplementary Video 4

H2 gas bubble evolution in 1 M HClO4 at −0.16 VRHE.

Supplementary Video 5

H2 microbubble coalescence at the initiation of a cycle in 1 M HCl.

Supplementary Video 6

H2 microbubble coalescence differences in different conditions.

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Park, S., Liu, L., Demirkır, Ç. et al. Solutal Marangoni effect determines bubble dynamics during electrocatalytic hydrogen evolution. Nat. Chem. 15, 1532–1540 (2023). https://doi.org/10.1038/s41557-023-01294-y

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