Increasing the potential window of the interface between two immiscible electrolyte solutions to more than 1.2V

Cousens, Nico E. A.; Kucernak, Anthony

doi:10.1016/j.elecom.2011.10.015

Cited by 19 publications

(21 citation statements)

References 19 publications

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“…A wider potential window can be achieved with highly hydrophobic organic and hydrophilic aqueous salts in solution. 45 In this sense, both LiCl and BTPPATFPB are well established aqueous and organic electrolytes, respectively. The choice of the organic solvent also changes the working window since it affects the affinity of electrolytes from both phases.…”

Section: Resultsmentioning

confidence: 99%

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Husmann

Booth

Zarbin

et al. 2018

J. Braz. Chem. Soc.

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The iron complex hexacyanoferrate (Fe 4 [Fe(CN) 6 ] 3 ), known as Prussian Blue (PB), was electrodeposited over a free-standing carbon nanotube (CNT) film assembled at the interface between two immiscible liquids, water and 1,2-dichlorobenzene. Polarization of the interface achieved through a fixed potential or under potential variation enabled iron present inside CNTs to generate a stable CNT/PB composite. We report herein on the observation that the deposition of PB is dependent on both the pH and applied potential. It was found that aqueous phases containing K 3 [Fe(CN) 6 ] can decompose under an applied potential, while those containing K 4 [Fe(CN) 6 ] presented more stable behavior making it a suitable precursor for PB synthesis. The electrodeposition and modification of the interface was followed by in situ spectroelectrochemical Raman spectroscopy, which indicated that an increase in signal due to PB formation was acompanied by changes in the CNT bands due to modification of the CNT walls by decoration with PB, forming a composite structure. Keywords: liquid-liquid interface, Prussian Blue, carbon nanotubes, immiscible liquids IntroductionBiphasic liquid/liquid (L/L) systems have been used for a long time, either for the study of interfacial electron and ion transfer reactions or for the synthesis and assembly of micro and nano-sized materials.1,2 The interface between two immiscible liquids provides a defect-free environment suitable for controlled homogeneous particle deposition. Driven by the decrease in the L/L interfacial free energy, particles dispersed or synthesized in a biphasic system spontaneously migrate to the interface formed by the two liquids. [3][4][5] Due to the ease of formation and robust nature of L/L interfaces, they have been utilized in a wide range of different applications. The L/L system can be used simply as a means to assemble previously synthesized materials into organized arrays or thin films, such as carbon nanostructures or metal nanoparticles. 6,7 Alternatively, materials can be both synthesized and assembled by using the L/L interface as the region of contact between reactants located in the different phases. [8][9][10] As an alternative to spontaneous reactions occurring at the point of contact between the two phases, material deposition can also occur by electrochemical polarization of the interface. 11,12 In addition to standard synthetic parameters such as concentration, time or pH, the applied potential and polarization of the interface between the two immiscible electrolyte solutions (ITIES) governs the rate of ion and electron transfer between the phases, allowing significant control over synthetic procedures. 1,2,13,14 By combining these different approaches to utilize the L/L interface, composite structures can be prepared using one material as the support and/or nucleation site for the other. 15,16 Previously, it has been observed that particle or polymer formation was possible, under stirring, on the surface of carbon nanostructures present in a L/L sy...

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Section: Resultsmentioning

confidence: 99%

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Husmann

Booth

Zarbin

et al. 2018

J. Braz. Chem. Soc.

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“…From the previous reports, some fundamental factors regarding of controlling the potential windows at an ITIES can be summarized as follows [34]: (1) Figures 1C and 1D which have similar phenomena but leading to wider potential windows for the same ketone. The isomers of straight-chain ketone have similar densities, permittivity, and solubility.…”

Section: Potential Windows For Heptanones and Nonanones With Two Orgamentioning

confidence: 98%

“…Therefore, the differences in interfacial structures lead to the different ion-transfer energies of supporting electrolytes. The potential window can be further increased via lowering the permittivity of the organic solvent [34]. The potential windows for ten derivatives of ketones are summarized in Table 1.…”

Section: Potential Windows For Heptanones and Nonanones With Two Orgamentioning

confidence: 99%

Electrochemical study of ketones as organic phases for the establishment of micro-liquid/liquid interfaces

Zhang

et al. 2016

Journal of Electroanalytical Chemistry

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“…As most inorganic ions are very hydrophilic, the Gibbs energy of ion transfer across ITIES is too high to be observed in the potential window of the investigated ITIES system. To solve the problem, one solution is to widen the potential window by using more hydrophilic salts in the aqueous phase and more hydrophobic slats in the organic phase as the supporting electrolytes . In our experience, for the commercially available organic supporting electrolyte (tetrabutylammonium tetrakis(4‐chlorophenyl)borate, BTPPA‐TPBCl), the potential window of the W/1,2‐DCE interface can reach more than 0.8 V when Li 2 SO 4 is used as the supporting electrolyte in aqueous solution.…”

Section: Introductionmentioning

confidence: 99%

“…For example, valinomycin was demonstrated as a good ligand for potassium cations . Owing to the development of supramolecular chemistry, various crown ethers, calixarenes, and polyethers were adopted as the ligands for different cations . However, there are only a few reports on the facilitated anion transfer (FAT) across ITIES, owing to the difficult availability of anion ligands .…”

Section: Introductionmentioning

confidence: 99%

Solvation Effect Facilitates Ion Transfer across Water/1,2‐Dichloroethane Interface

et al. 2016

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Ion transfer across the interface between two immiscible electrolytes can produce a Faraday current involving non‐redox reactions, which is useful for both ion detection and phase‐transfer catalysis. To decrease the transfer energy and improve the selectivity, artificial ligands are needed, which are usually unavailable because of the difficulty in the synthesis. Herein, we demonstrate that the solvation effect can act as the driving force for ion transfer across the micropipette‐supported water/1,2‐dichloroethane interface, including the anions SO42−, NO3−, NO2−, CO32−, and so forth. The thermodynamic properties are discussed, including the diffusion coefficients, Gibbs energy of ion transfer, stoichiometric ratios, and apparent association constants. Meanwhile, the research also provides a method to investigate the solvation effect.

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Increasing the potential window of the interface between two immiscible electrolyte solutions to more than 1.2V

Cited by 19 publications

References 19 publications

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Electrochemical study of ketones as organic phases for the establishment of micro-liquid/liquid interfaces

Solvation Effect Facilitates Ion Transfer across Water/1,2‐Dichloroethane Interface

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