Electrochemical Stability of Zinc and Copper Surfaces in Protic Ionic Liquids

Ionic liquids are versatile solvents that can be tailored through modification of the cation and anion species. Relatively little is known about the corrosive properties of protic ionic liquids. In this study, we have explored the corrosion of both zinc and copper within a series of protic ionic liq...

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Published inLangmuir Vol. 38; no. 15; pp. 4633 - 4644
Main Authors Greaves, Tamar L, Dharmadana, Durga, Yalcin, Dilek, Clarke-Hannaford, Jonathan, Christofferson, Andrew J, Murdoch, Billy J, Han, Qi, Brown, Stuart J, Weber, Cameron C, Spencer, Michelle J. S, McConville, Chris F, Drummond, Calum J, Jones, Lathe A
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 19.04.2022
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Abstract Ionic liquids are versatile solvents that can be tailored through modification of the cation and anion species. Relatively little is known about the corrosive properties of protic ionic liquids. In this study, we have explored the corrosion of both zinc and copper within a series of protic ionic liquids consisting of alkylammonium or alkanolammonium cations paired with nitrate or carboxylate anions along with three aprotic imidazolium ionic liquids for comparison. Electrochemical studies revealed that the presence of either carboxylate anions or alkanolammonium cations tend to induce a cathodic shift in the corrosion potential. The effect in copper was similar in magnitude for both cations and anions, while the anion effect was slightly more pronounced than that of the cation in the case of zinc. For copper, the presence of carboxylate anions or alkanolammonium cations led to a notable decrease in corrosion current, whereas an increase was typically observed for zinc. The ionic liquid–metal surface interactions were further explored for select protic ionic liquids on copper using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to characterize the interface. From these studies, the oxide species formed on the surface were identified, and copper speciation at the surface linked to ionic liquid and potential dependent surface passivation. Density functional theory and ab initio molecular dynamics simulations revealed that the ethanolammonium cation was more strongly bound to the copper surface than the ethylammonium counterpart. In addition, the nitrate anion was more tightly bound than the formate anion. These likely lead to competing effects on the process of corrosion: the tightly bound cations act as a source of passivation, whereas the tightly bound anions facilitate the electrodissolution of the copper.
AbstractList Ionic liquids are versatile solvents that can be tailored through modification of the cation and anion species. Relatively little is known about the corrosive properties of protic ionic liquids. In this study, we have explored the corrosion of both zinc and copper within a series of protic ionic liquids consisting of alkylammonium or alkanolammonium cations paired with nitrate or carboxylate anions along with three aprotic imidazolium ionic liquids for comparison. Electrochemical studies revealed that the presence of either carboxylate anions or alkanolammonium cations tend to induce a cathodic shift in the corrosion potential. The effect in copper was similar in magnitude for both cations and anions, while the anion effect was slightly more pronounced than that of the cation in the case of zinc. For copper, the presence of carboxylate anions or alkanolammonium cations led to a notable decrease in corrosion current, whereas an increase was typically observed for zinc. The ionic liquid-metal surface interactions were further explored for select protic ionic liquids on copper using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to characterize the interface. From these studies, the oxide species formed on the surface were identified, and copper speciation at the surface linked to ionic liquid and potential dependent surface passivation. Density functional theory and ab initio molecular dynamics simulations revealed that the ethanolammonium cation was more strongly bound to the copper surface than the ethylammonium counterpart. In addition, the nitrate anion was more tightly bound than the formate anion. These likely lead to competing effects on the process of corrosion: the tightly bound cations act as a source of passivation, whereas the tightly bound anions facilitate the electrodissolution of the copper.
Author Weber, Cameron C
Jones, Lathe A
Han, Qi
Dharmadana, Durga
Spencer, Michelle J. S
Clarke-Hannaford, Jonathan
Brown, Stuart J
Christofferson, Andrew J
Murdoch, Billy J
Drummond, Calum J
Yalcin, Dilek
McConville, Chris F
Greaves, Tamar L
AuthorAffiliation CAMIC, Centre for Advanced Materials and Industrial Chemistry
School of Science, STEM College
The MacDiarmid Institute for Advanced Materials and Nanotechnology
ARC Centre of Excellence in Exciton Science, School of Science
ARC Centre of Excellence in Future Low-Energy Electronics Technologies, School of Science
CSIRO Manufacturing
Centre for Materials and Surface Science, Department of Chemistry and Physics, School of Molecular Sciences
La Trobe University
RMIT Microscopy and Microanalysis Facility, STEM College
School of Chemical Sciences
RMIT University Library
Institute for Frontier Materials
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crossref_primary_10_1002_admi_202202110
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Snippet Ionic liquids are versatile solvents that can be tailored through modification of the cation and anion species. Relatively little is known about the corrosive...
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Title Electrochemical Stability of Zinc and Copper Surfaces in Protic Ionic Liquids
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