Linking the Cu(II/I) potential to the onset of dynamic phenomena at corroding copper microelectrodes immersed in aqueous 0.5 M NaCl

Langley, Amelia R.; Carta, Mariolino; Malpass‐Evans, Richard; McKeown, Neil B.; Dawes, Jonathan; Murphy, Ellen; Marken, Frank

doi:10.1016/j.electacta.2017.12.083

Cited by 9 publications

(23 citation statements)

References 26 publications

(27 reference statements)

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“…SCE is observed associated with the formation of CuCl (see equation 1). The thickness of this passive film has been reported to be typically 0.4 μm . A second anodic peak is observed at approx.…”

Section: Resultsmentioning

confidence: 99%

“…The second anodic peak and commencement of current noise have been linked to sub‐interfacial Cu(II) formation at the Cu|CuCl interface causing instabilities in the passive film . Current spikes are also observed (up to 40 μA in magnitude), representing CuCl film breakdown and colloidal dissolution events of the CuCl film . This process has been shown to be dependent on the presence of dissolved gases in the solution phase, probably due to gas bubble nucleation and implosion during breakdown .…”

Section: Resultsmentioning

confidence: 99%

“…The first anodic peak at 0.0 V vs . SCE is attributed to CuCl formation (equation 1) . The second anodic peak at approx.…”

Section: Resultsmentioning

confidence: 99%

“…0.2 V vs. SCE is attributed to the formation of Cu(II) causing strain in the passive film and leading to instabilities observed as current noise thereafter (see Figure 1a-c). [15,34] For constantan, only one anodic peak is observed at approx. 0.2 V vs. SCE during the first cycle (see Figure 3b).…”

Section: Resultsmentioning

confidence: 99%

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Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

et al. 2020

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Copper and copper–nickel alloys are known to form partially passive films in marine conditions, both naturally and under positive potential bias. Here, the anodic passivation behaviour of copper and of constantan (Cu54Ni45Mn1) as a model for a copper‐nickel alloy are investigated and compared at high positive overpotentials and in 0.5 M NaCl(aq). Abrupt potential‐dependent passive film breakdown is observed for both Cu and Cu−Ni alloys during voltammetry and during chronoamperometry experiments. For Cu, a single transitions occurs at 0.2 V vs. SCE consistent with a Cu(II/I) process, leading to interfacial stress and breaking of a passive CuCl film. For Cu−Ni alloy, two stages are observed at 0.3 V vs. SCE due to a Cu(II/I) process and at 1.7 V vs. SCE due to a sub‐interfacial Ni(IV/II) process. A breakdown mechanism is proposed based on redox processes at the buried interface at the metallic conductor | passive ion conductor junction.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…The first anodic peak at 0.0 V vs . SCE is attributed to CuCl formation (equation 1) . The second anodic peak at approx.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

et al. 2020

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“…PIM materials that allow protonation also gave novel ionic diode (or rectification) effects, and this was then suggested to lead to opportunities for example in novel desalination processes . PIM materials were employed to stabilise nanoparticulate catalysts, and to affect the pathway of corrosion processes . PIM‐1 has been shown to produce electrochemiluminescence effects in aqueous media .…”

Section: Introductionmentioning

confidence: 99%

Triphasic Nature of Polymers of Intrinsic Microporosity Induces Storage and Catalysis Effects in Hydrogen and Oxygen Reactivity at Electrode Surfaces

et al. 2018

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Hydrogen oxidation and oxygen reduction are two crucial energy conversion reactions, which are shown to be both strongly affected by the presence of intrinsically microporous polymer coatings on electrodes. Polymers of intrinsic microporosity (PIMs) are known to possess extremely high internal surface area and ability to bind gases under dry conditions. It is shown here that both, hydrogen‐ and oxygen gas binding into PIMs, also occurs under wet or “triphasic” conditions in aqueous electrolyte environments (when immersed in 0.01 M phosphate buffer at pH 7). For two known PIM materials (PIM‐1 and PIM‐PY), nanoparticles are formed by an anti‐solvent precipitation protocol and then cast as a film onto platinum or glassy carbon electrodes. Voltammetry experiments reveal evidence for hydrogen and oxygen binding. Both, PIM‐1 and PIM‐PY, locally store hydrogen or oxygen gas at the electrode surface and thereby significantly affect electrocatalytic reactivity. The onset of oxygen reduction on glassy carbon is shifted by 0.15 V in the positive direction.

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A New Type of Supramolecular Fluid Based on H₂O–Alkylammonium/Phosphonium Solutions

et al. 2021

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Here we show that by adjusting the concentration of tetrabutyl ammonium and phosphonium salts in water (% 1.5-2.0 m), hydrophobic solvation triggers the formation of a unique, highly incompressible supramolecular liquid, with a dynamic structure similar to clathrates, involving essentially all H 2 O molecules of the solvent. Despite the increasing local order, the thermal diffusivity, and compressibility of these supramolecular liquids is strongly decreased with respect to bulk water due to slower relaxation dynamics. The results presented in this paper open an avenue to design a new family of supramolecular fluids, stable under atmospheric conditions, which can find important technological applications in energy storage and conversion. Dissolving small non (or moderate)-polar molecules in water induces the formation of local ice-like structures around them. [1-4] Above a certain concentration of the solute, and under conditions of high pressure and low temperature, these host-guest hydrates can form crystalline solids, so-called clathrate hydrates, a vast class of materials with important applications in gas separation, storage and transportation. [5-7] When the host molecule takes part within the multi-polyhedral structure of hydrogen-bonded water, semi-clathrate hydrates are formed. This is the case for tetrabutyl ammonium bromide (TtBABr) and other quaternary ammonium salts, in which the anions incorporate into

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Linking the Cu(II/I) potential to the onset of dynamic phenomena at corroding copper microelectrodes immersed in aqueous 0.5 M NaCl

Cited by 9 publications

References 26 publications

Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

Triphasic Nature of Polymers of Intrinsic Microporosity Induces Storage and Catalysis Effects in Hydrogen and Oxygen Reactivity at Electrode Surfaces

A New Type of Supramolecular Fluid Based on H₂O–Alkylammonium/Phosphonium Solutions

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Linking the Cu(II/I) potential to the onset of dynamic phenomena at corroding copper microelectrodes immersed in aqueous 0.5 M NaCl

Cited by 9 publications

References 26 publications

Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

Linking the Cu(II/I) and the Ni(IV/II) Potentials to Subsequent Passive Film Breakdown for a Cu−Ni Alloy in Aqueous 0.5 M NaCl

Triphasic Nature of Polymers of Intrinsic Microporosity Induces Storage and Catalysis Effects in Hydrogen and Oxygen Reactivity at Electrode Surfaces

A New Type of Supramolecular Fluid Based on H2O–Alkylammonium/Phosphonium Solutions

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Product

Resources

About

Linking the Cu(II/I) potential to the onset of dynamic phenomena at corroding copper microelectrodes immersed in aqueous 0.5 M NaCl

A New Type of Supramolecular Fluid Based on H₂O–Alkylammonium/Phosphonium Solutions