On the non-ideal behaviour of polarised liquid-liquid interfaces

Suárez-Herrera, Marco F.; Scanlon, Micheál D.

doi:10.1016/j.electacta.2019.135110

Cited by 26 publications

(48 citation statements)

References 55 publications

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“…Controlled assembly of molecules and nano-objects and in situ electrogeneration of nanomaterials and membranes are possible [10]. It was shown that the Galvani potential difference at the ITIES can be effectively used to manipulate the reactivity of gold nanoparticles by varying the Fermi level (both chemically and electrochemically) or the position of nanoparticles at the liquid-liquid interface [62][63][64]. It was established that the classical electroanalytical method with a solid electrode can be directly transferred to ITIES, which makes it possible to easily trace and interpret reversible charge transfer reactions [65].…”

Section: Interfacial Formationsmentioning

confidence: 99%

Interfacial Synthesis: Morphology, Structure, and Properties of Interfacial Formations in Liquid–Liquid Systems

Golubina

Kizim

2021

Russ. J. Phys. Chem.

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The results of studies in the field of interfacial synthesis and interfacial formations in liquid–liquid systems are summarized. The mechanisms of the processes of interfacial synthesis are considered. Data on the self-assembly of nanoparticles, films, and 3D materials are given. The properties of materials of interfacial formations in systems with rare-earth elements and di(2-ethylhexyl)phosphoric acid, obtained both in the presence and absence of local vibrations, are described. It was established that materials obtained in the presence of local vibrations in the interfacial layer have higher density, melting point, and magnetic susceptibility and lower electric conductivity. The effect of force field parameters on the properties of interfacial formations is considered. Practical applications and prospects for research in the field of interfacial formations are discussed.

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Section: Interfacial Formationsmentioning

confidence: 99%

Interfacial Synthesis: Morphology, Structure, and Properties of Interfacial Formations in Liquid–Liquid Systems

Golubina

Kizim

2021

Russ. J. Phys. Chem.

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“…Considering that TMA + transfers close to the PZC (compare Figures 2B and C), a low influence of the electrical double layer was expected as the impact of migration should be negligible. [9,34] The interfacial AuNP film was found to have no significant effect on the TMA + ion transfer kinetics as demonstrated by (i) the peak separation of the reversible TMA + ion transfer response being 58 mV ( Figure 2C), (ii) the ion transfer resistance being undetectable by EIS experiments ( Figure 2D), and (iii) the Randles circuit accurately describing the EIS spectra at the TMA + ion transfer potential of +0.311 V ( Figure 2D).…”

Section: The Dotted Lines Inmentioning

confidence: 99%

“…Taking into account that  o w  affects EF(AuNPs), as discussed due to the adsorption of OH -, it is going to also affect the kinetics of the electron transfer reactions according to Equation (9).…”

Section: Biphasic Oxidation Of Elemental Sulfur Catalysed By Interfacialmentioning

confidence: 99%

“…[8] A powerful approach to mimic and model such processes, involving simultaneous ion and electron transfer reactions, is to electrochemically polarize an interface between two immiscible electrolyte solutions (ITIES). [9][10][11] Electrochemical reactions at such polarized liquid|liquid (L|L) interfaces may be complex due to the simultaneous coupling of not only interfacial ion and electron transfer reactions but also homogeneous chemical reactions, interfacial adsorption of ions or neutral species and the transport of solvent molecules across the interface by diffusion or facilitated by ion transfer. [12] In the absence of a microorganism, the activation energy to form sulfate from S8, molecular oxygen (O2) and water is prohibitively high at ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

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Mimicking the Microbial Oxidation of Elemental Sulfur with a Biphasic Electrochemical Cell

Suárez-Herrera¹,

Sollá-Gullón²,

Scanlon

2021

Preprint

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The lack of an artificial system that mimics elemental sulfur (S8) oxidation by microorganisms inhibits a deep mechanistic understanding of the sulfur cycle in the biosphere and the metabolism of sulfur-oxidizing microorganisms. In this article, we present a biphasic system that mimics biochemical sulfur oxidation under ambient conditions using a liquid|liquid (L|L) electrochemical cell and gold nanoparticles (AuNPs) as an interfacial catalyst. The interface between two solvents of very different polarity is an ideal environment to oxidise S8, overcoming the <a>incompatible solubilities </a>of the hydrophobic reactants (O2 and S8) and hydrophilic products (H+, SO32–, SO42–, etc.). The interfacial AuNPs provide a catalytic surface onto which O2 and S8 can adsorb. Control over the driving force for the reaction is provided by polarizing the L|L interface externally and tuning the Fermi level of the interfacial AuNPs by the adsorption of aqueous anions.

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“…Differential capacitance measurements are a macroscopic view of the charge distribution of the back-to-back diffusion layer or mixed solvent region. 23,[37][38][39][40][41] The capacitance minimum appears at the potential of zero charge (PZC). Figure S4a where the Faradaic current due to ion transfer of tetraethylammonium cations across a bare water|TFT interface was entirely filtered out at 80 Hz.…”

Section: Electrochemistry Of the Floating Film Of Znpor-ins At The Itiesmentioning

confidence: 99%

Reversible Electrochemical Ion Intercalation at an Electrified Liquid|liquid Interface Functionalised with Porphyrin Nanostructures

Molina-Osorio¹,

Manzanares²,

Gamero‐Quijano³

et al. 2020

Preprint

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<a>Ion intercalation into solid matrices influences the performance of key components in most energy storage devices (Li-ion batteries, supercapacitors, fuel cells, etc.). Electrochemical methods provide key information on the thermodynamics and kinetics of these ion transfer processes but are restricted to matrices supported on electronically conductive substrates. In this article, the electrified liquid|liquid interface is introduced as an ideal platform to probe the thermodynamics and kinetics of reversible ion intercalation with non-electronically active matrices. Zinc(II) meso-tetrakis(4-carboxyphenyl)porphyrins were self-assembled into floating films of ordered nanostructures at the water|</a>a,a,a-trifluorotoluene interface. Electrochemically polarising the aqueous phase negatively with respect to the organic phase lead to organic ammonium cations intercalating into the zinc porphyrin nanostructures by binding to anionic carboxyl sites and displacing protons through ion exchange at neutral carboxyl sites. The cyclic voltammograms suggested a positive cooperativity mechanism for ion intercalation linked with structural rearrangements of the porphyrins within the nanostructures, and were modelled using a Frumkin isotherm. The model also provided a robust understanding of the dependence of the voltammetry on the pH and organic electrolyte concentration. Kinetic analysis was performed using potential step chronoamperometry, with the current transients composed of “adsorption” and nucleation components. The latter were associated with domains within the nanostructures where, due to structural rearrangments, ion binding and exchange took place faster. This work opens opportunities to study the thermodynamics and kinetics of purely ionic ion intercalation reactions (not induced by redox reactions) in floating solid matrices using any desired electrochemical method.

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On the non-ideal behaviour of polarised liquid-liquid interfaces

Cited by 26 publications

References 55 publications

Interfacial Synthesis: Morphology, Structure, and Properties of Interfacial Formations in Liquid–Liquid Systems

Interfacial Synthesis: Morphology, Structure, and Properties of Interfacial Formations in Liquid–Liquid Systems

Mimicking the Microbial Oxidation of Elemental Sulfur with a Biphasic Electrochemical Cell

Reversible Electrochemical Ion Intercalation at an Electrified Liquid|liquid Interface Functionalised with Porphyrin Nanostructures

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