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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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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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.
The authors declare no competing interests.
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Supplementary Notes 1 and 2, Figs. 1–17, Table 1 and References.
H2 gas bubble evolution in 1 M H2SO4 at −0.16 VRHE.
H2 gas bubble evolution in 1 M HCl at −0.16 VRHE.
H2 gas bubble evolution in 1 M HNO3 at −0.16 VRHE.
H2 gas bubble evolution in 1 M HClO4 at −0.16 VRHE.
H2 microbubble coalescence at the initiation of a cycle in 1 M HCl.
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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