Bond breaking electron transfer across a conducting nanowire(nanotube)/electrolyte solution interface: The role of electrical double layer effects

Nazmutdinov, Renat R.; Bronshtein, Michael D.; Березин, А. С.; Soldano, Germán; Schmickler, Wolfgang

doi:10.1016/j.jelechem.2011.01.001

Cited by 8 publications

(15 citation statements)

References 39 publications

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“…Another challenging problem is the influence the electrode charge (i. e. the electrical double layer effect) on the kinetics of heterogeneous electron transfer in nanoconfined electrolyte solutions. This effect was addressed recently in works [50,51] for the reduction of anions on the outside of charged conducting nanocylinders by solving the Poisson‐Boltzmann equation. As some intriguing kinetic features were predicted for such electrochemical systems, it would be worth to extend these model studies to redox processes within carbon nanotubes.…”

Section: Discussionmentioning

confidence: 99%

Confinement Effect on Heterogeneous Electron Transfer in Aqueous Solutions inside Conducting Nanotubes

et al. 2021

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An Fe3+/2+ redox couple in conducting single wall carbon nanotubes filled with water molecules is investigated in the framework of the electron transfer theory and with classical molecular dynamics simulations. The diameter of the nanotubes ranges from 0.8 nm to 3.5 nm. It can be concluded, qualitatively, that the electron transfer rate significantly increases with decreasing nanotube diameter. This effect is explained basically in terms of the solvent reorganization energy. Other factors that can affect the reaction rate are discussed as well.

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Section: Discussionmentioning

confidence: 99%

Confinement Effect on Heterogeneous Electron Transfer in Aqueous Solutions inside Conducting Nanotubes

et al. 2021

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“…Refs. cited in works 3,9 ), the authors investigated the averaged properties of arrays of carbon nanotubes and metal nanowires. Reliable kinetic measurements on a single nanosize electrode remain still an exceedingly complicated and challenging problem.…”

Section: Discussionmentioning

confidence: 99%

“…3,[6][7][8][9] on the basis of quantum mechanical theory 10,11 . Some qualitatively interesting features were predicted for the [Fe(CN) 6 ] 3-/4redox couple 3 (electrostatic catalysis, inverted Arrhenius plot) and the reduction of peroxodisulphate anion 9 (disappearance of a "pit" in current -voltage curves observed in diluted supporting electrolyte solutions). Sizable catalytic effects were predicted when considering the hydrogen evolution on different metal nanowires 7,8 .…”

Section: Introductionmentioning

confidence: 99%

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Orbital Overlap Effects in Electron Transfer Reactions across a Metal Nanowire/Electrolyte Solution Interface

et al. 2013

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In this communication we report on calculations of the orbital overlap between Fe(III) and Cr(III) aquacomplexes and different electrode surfaces: Cu(111), Ag (111), Au(111), Pt(111), and corresponding monoatomic wires. The electronic structure of the monocrystalline surfaces and nanowires are described in terms of the electronic spillover and density of electronic states at the Fermi level obtained from periodic Density Functional Theory (DFT) calculations. The transmission coefficients (κ ) characterizing the first stage of outer-sphere electron transfer for the reduction of aquacomplexes are calculated on the basis of Landau-Zener theory as a function of electrodereactant separation; the electronic transmission coefficients for the [Cr(H 2 O) 6 ] 3+/2+ redox couple were found to be smaller than those for [Fe(H 2 O) 6 ] 3+/2+ . Two different intervals can be clearly distinguished for Cu, Au and Pt: "a catalytic region", where κ (wire) > κ (Me slab) and "an inhibition region", where κ (wire) < κ (Me slab). A similar behaviour exhibits the coupling constant estimated for a hydrogen atom adsorbed at the Au(111) surface and the Au monoatomic wire. These effects originate from some specific features of electronic density profile for metal nanowires: at short distances the electronic density of nanowires is higher compared with the (111) metal surfaces, while at larger separations it decreases more sharply.

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“…nanotubes modeled 61,62 with intriguing expectations such as inverse Arrhenius behavior and disappearance of a "pit" in the current-voltage relations. Reactantmonoatomic metal (Ag, Au, Cu, Pt) nanowire orbital overlap for the [Fe(OH 2 ) 6 ] 3+/2+ and [Cr(OH 2 ) 6 ] 3+/2+ couples in aqueous solution has further been addressed by quantum mechanical theory 63 .…”

Section: Accepted Manuscriptmentioning

confidence: 92%

Electrochemistry of single molecules and biomolecules, molecular scale nanostructures, and low-dimensional systems

Nazmutdinov

Zinkicheva

Shermukhamedov

et al. 2018

Current Opinion in Electrochemistry

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Bond breaking electron transfer across a conducting nanowire(nanotube)/electrolyte solution interface: The role of electrical double layer effects

Cited by 8 publications

References 39 publications

Confinement Effect on Heterogeneous Electron Transfer in Aqueous Solutions inside Conducting Nanotubes

Confinement Effect on Heterogeneous Electron Transfer in Aqueous Solutions inside Conducting Nanotubes

Orbital Overlap Effects in Electron Transfer Reactions across a Metal Nanowire/Electrolyte Solution Interface

Electrochemistry of single molecules and biomolecules, molecular scale nanostructures, and low-dimensional systems

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