The corona of a surface bubble promotes electrochemical reactions

Yan B. Vogel; Cameron W. Evans; Mattia Belotti; Longkun Xu; Isabella C. Russell; Li Juan Yu; Alfred K.K. Fung; Nicholas S. Hill; Nadim Darwish; Vinicius R. Gonçales; Michelle L. Coote; K. Swaminathan Iyer; Simone Ciampi

doi:10.1038/s41467-020-20186-0

The corona of a surface bubble promotes electrochemical reactions

Yan B. Vogel, Cameron W. Evans, Mattia Belotti, Longkun Xu, Isabella C. Russell, Li Juan Yu, Alfred K.K. Fung, Nicholas S. Hill, Nadim Darwish, Vinicius R. Gonçales, Michelle L. Coote, K. Swaminathan Iyer, Simone Ciampi

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Abstract

The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode’s surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.

Original language	English
Article number	6323
Number of pages	8
Journal	Nature Communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-20186-0
Publication status	Published - 10 Dec 2020
Externally published	Yes

Bibliographical note

Funding Information:
S.C., N.D., and M.L.C. were supported by the Australian Research Council (grant nos. DP190100735, FT190100148, FL170100041, and CE140100012). M.L.C. acknowledges generous supercomputing time from the National Computational Infrastructure. C.W.E. and K.S.I. acknowledge the facilities and technical assistance of Microscopy Australia at the Centre for Microscopy, Characterisation & Analysis, The University of Western Australia, a facility funded by the University, State and Commonwealth Governments.

Publisher Copyright:
© 2020, The Author(s).

Keywords

Corona
Surface Bubble
Electrochemical Reactions

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Vogel_Corona_P2020Final published version, 1.41 MBLicence: CC BY

Cite this

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title = "The corona of a surface bubble promotes electrochemical reactions",

abstract = "The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode{\textquoteright}s surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.",

keywords = "Corona, Surface Bubble, Electrochemical Reactions",

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note = "Funding Information: S.C., N.D., and M.L.C. were supported by the Australian Research Council (grant nos. DP190100735, FT190100148, FL170100041, and CE140100012). M.L.C. acknowledges generous supercomputing time from the National Computational Infrastructure. C.W.E. and K.S.I. acknowledge the facilities and technical assistance of Microscopy Australia at the Centre for Microscopy, Characterisation & Analysis, The University of Western Australia, a facility funded by the University, State and Commonwealth Governments. Publisher Copyright: {\textcopyright} 2020, The Author(s).",

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AU - Evans, Cameron W.

AU - Belotti, Mattia

AU - Xu, Longkun

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AU - Yu, Li Juan

AU - Fung, Alfred K.K.

AU - Hill, Nicholas S.

AU - Darwish, Nadim

AU - Gonçales, Vinicius R.

AU - Coote, Michelle L.

AU - Swaminathan Iyer, K.

AU - Ciampi, Simone

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N2 - The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode’s surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.

AB - The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode’s surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.

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ER -

The corona of a surface bubble promotes electrochemical reactions

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Keywords

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