Nanostructure of the deep eutectic solvent/platinum electrode interface as a function of potential and water content

Hammond, Oliver S.; Li, Hua; Westermann, Christian; Al-Murshedi, Azhar Y. M.; Endres, Frank; Abbott, Andrew P.; Warr, Gregory G.; Edler, Karen J.; Atkin, Rob

doi:10.1039/c8nh00272j

Cited by 72 publications

(76 citation statements)

References 72 publications

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“…However, one must bear in mind that the addition of small amounts of water may also lead to changes in Ni 2þ complexation, as well as in the structure of the electrolyte, in the bulk, and at the interface. Recently it has been shown that H 2 O content significantly influences the interactions of DES constituents (water, choline, urea, chloride and nickel) [41,44,45]. Therefore, it is known that the increase of water content from 0.1 wt% to 2.1 wt% (or to 0.25 wt% in blank electrolyte) changes the interactions between water and DES components by possibly increasing the electrolyte integrity, which occurs by strengthening the Ch þ -Cl e interactions [42].…”

Section: Resultsmentioning

confidence: 99%

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Influence of water content and applied potential on the electrodeposition of Ni coatings from deep eutectic solvents

Łukaczyńska

Cherigui

Ceglia

et al. 2019

Electrochimica Acta

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Ni coatings were electrodeposited from 1:2 choline chloride (ChCl)-urea (U) deep eutectic solvents (DESs) on low carbon steel. We report on the interrelated influence of water content in the electrolyte and applied potential on the formation of Ni films and their chemical composition and morphology. This was investigated by cyclic voltammetry (CV) and chronoamperometry (CA) in combination with ex-situ characterization techniques (FE-SEM, EDS, XPS and Raman spectroscopy). Ni electrodeposition from DES is shown to be highly complex: Ni þ2 reduction is followed by water reduction, which triggers electrolyte decomposition. A water content higher than 4.5%wt and/or performing electrodeposition at potentials more negative than E ¼ À0:90V vs Ag quasi-reference electrode enhances the decomposition of the solvent. This breakdown appears via either an electrochemical reaction or triggered by water splitting. In both cases, it leads to the incorporation of DESs decomposition products, such as trimethylamine and acetaldehyde within the Ni film. Under these conditions, the films are composed of metallic Ni and NiO x (OH) 2(1Àx) .

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Section: Resultsmentioning

confidence: 99%

“…In both cases, changes of the interfacial structure (i.e. higher concentration of water molecules) could also have an effect, although not yet possible to predict in which direction [45].…”

Section: Resultsmentioning

confidence: 99%

Influence of water content and applied potential on the electrodeposition of Ni coatings from deep eutectic solvents

Łukaczyńska

Cherigui

Ceglia

et al. 2019

Electrochimica Acta

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“…X-ray reflectometry (XRR) studies of different ionic liquid-solid interfaces were performed by several research groups 21 confirming the layering of ions on sapphire, 22,23 gold, 24 and silicon 25 surfaces. However, as stated in Hammond et al, 26 based on their investigation, it appears that conclusions obtained for ionic liquid systems will not necessarily be valid for DESs. Their atomic force microscopy study of a DES/platinum interface reveals that adding water to a DES has an unexpected effect on the interface, actually increasing the interfacial nanostructure by up to 40%.…”

Section: Introductionmentioning

confidence: 87%

Revealing the interfacial nanostructure of a deep eutectic solvent at a solid electrode

Zec

Mangiapia

Zheludkevich

et al. 2020

Phys. Chem. Chem. Phys.

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“…The influence of water and the changing potential on the interfacial region between a platinum electrode and a DES were studied. It was found that the nanostructural feature of interface decreased in the presence of small amount of water and was also strongly potential dependent [23].The aim of this work is to investigate the dissolution mechanism of copper in a DES and its comparable IL and compare it to the aqueous system. This is important for counter-electrode processes during electrodeposition, for electropolishing, and also to understand whether metallic copper corrodes in the DESs.…”

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confidence: 99%

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The Anodic Behaviour of Bulk Copper in Ethaline and 1-Butyl-3-Methylimidazolium Chloride

et al. 2019

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The anodic dissolution of bulk metallic copper was conducted in ionic liquids (ILs)-a deep eutectic solvent (DES) ((CH 3 ) 3 NC 2 H 4 OH) comprised of a 1:2 molar ratio mixture of choline chloride Cl (ChCl), and ethylene glycol (EG)-and imidazolium-based ILs, such as C 4 mimCl, using electrochemical techniques, such as cyclic voltammetry, anodic linear sweep voltammetry, and chronopotentiometry.To investigate the electrochemical dissolution mechanism, electrochemical impedance spectroscopy (EIS) was used. In addition to spectroscopic techniques, for instance, UV-visible spectroscopy, microscopic techniques, such as atomic force microscopy (AFM), were used. The significant industrial importance of metallic copper has motivated several research groups to deal with such an invaluable metal. It was confirmed that the speciation of dissolved copper from the bulk phase at the interface region is [CuCl 3 ] − and [CuCl 4 ] 2− in such chloride-rich media, and the EG determine the structure of the interfacial region in the electrochemical dissolution process. A super-saturated solution was produced at the electrode/solution interface and CuCl 2 was deposited on the metal surface.Gu et al. studied electrodeposition and the corrosion behaviour of copper in a choline chloride-ethylene glycol DES. In the electrodeposition process, a rough surface was obtained with the addition of ethylene diamine; the corrosion decreased and a relatively uniform surface was gained [5]. Many research groups have tried to deal with the physical properties of ethaline (choline chloride-ethylene glycol). it was found that the mass transport could be increased with an increasing temperature; when the temperature was increased to 50 • C, the viscosity decreased by 65% [7]. Concerning the physical properties of the electrolyte, such as conductivity and viscosity, it was found that it is insensitive to metal-salt addition but strongly temperature dependent [9]. The speciation of copper is well-defined in choline-based DESs. It was determined to be [CuCl 3 ] 2− and [CuCl 4 ] 2− for Cu(I) and Cu(II), respectively [20]. The dissolution of bulk copper was studied previously in these media, in the present work attempt was directed to deal with copper in more detail [21]. Deep eutectic solvents (DESs) are attracting significant research interest as electrochemical media, especially for electrodeposition, as they share many of the useful properties of ILs, but are typically greener and cheaper [22]. The influence of water and the changing potential on the interfacial region between a platinum electrode and a DES were studied. It was found that the nanostructural feature of interface decreased in the presence of small amount of water and was also strongly potential dependent [23].The aim of this work is to investigate the dissolution mechanism of copper in a DES and its comparable IL and compare it to the aqueous system. This is important for counter-electrode processes during electrodeposition, for electropolishing, and also to understand whether metallic co...

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Nanostructure of the deep eutectic solvent/platinum electrode interface as a function of potential and water content

Abstract: Addition of water increases the DES interfacial nanostructure up to ∼40 wt%. This differs starkly from ionic liquids, where addition of small amounts of water rapidly decreases the interfacial nanostructure.

Cited by 72 publications

References 72 publications

Influence of water content and applied potential on the electrodeposition of Ni coatings from deep eutectic solvents

Influence of water content and applied potential on the electrodeposition of Ni coatings from deep eutectic solvents

Revealing the interfacial nanostructure of a deep eutectic solvent at a solid electrode

The Anodic Behaviour of Bulk Copper in Ethaline and 1-Butyl-3-Methylimidazolium Chloride

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