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

Shermukhamedov, Shokirbek A.; Nazmutdinov, Renat R.; Bronshtein, Michael D.; Probst, Michael

doi:10.1002/celc.202001569

Cited by 7 publications

(14 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This conclusion is further supported by the enhanced decrease in λ for the parallel geometry, when both A and B are partly desolvated in the first layer. This stresses the importance of the interfacial solvation shell structure that has been recognized in other contexts [21,26,30,33] . As reviewed e.g.…”

Section: Dielectric Constant and Reorganization Energysupporting

confidence: 53%

“…This stresses the importance of the interfacial solvation shell structure, an aspect recognized in other contexts. [21,26,30,33] As reviewed e. g. in Ref. [57] this highlights an important limitation of dielectric continuum models which do not correctly describe these hydration structure changes at interfaces.…”

Section: Dielectric Constant and Reorganization Energymentioning

confidence: 99%

“…[28] In addition, λ may be influenced by modified interfacial solvation shell structure. [21,26,30,33] Here we are instead concerned with an aqueous solution model ET reaction confined between graphene surfaces, which do not involve such significant image charge effects; this allows a focus of attention on interfacial region (and beyond) solvation effects, including those related to water's dielectric constant behavior. In this first effort, we focus on an ET reaction not involving charge transfer to or from the graphene, but rather examine an ET for a solute within the water solvent.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Model Electron Transfer Reaction in Confined Aqueous Solution

2021

View full text Add to dashboard Cite

Liquid water confined within nanometer-sized channels exhibits a strongly reduced local dielectric constant perpendicularly to the wall, especially at the interface, and this has been suggested to induce faster electron transfer kinetics at the interface than in the bulk. We study a model electron transfer reaction in aqueous solution confined between graphene sheets with classical molecular dynamics. We show that the solvent reorganization energy is reduced at the interface compared to the bulk, which explains the larger rate constant. However, this facilitated solvent reorganization is due to the partial desolvation by the graphene sheet of the ions involved in the electron transfer and not to a local dielectric constant reduction effect.

show abstract

Section: Dielectric Constant and Reorganization Energysupporting

confidence: 53%

Section: Dielectric Constant and Reorganization Energymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Model Electron Transfer Reaction in Confined Aqueous Solution

2021

View full text Add to dashboard Cite

show abstract

“…The nanoconfined space formed in nanoporous Pt could also affect the properties of the solvent [13] . The rate of electron transfer may increase in nanoconfined space due to decreasing solvent reorganization energy [13d] …”

Section: Methodsmentioning

confidence: 99%

Selective Enhancement of Electrochemical Signal Based on the Size of Alcohols Using Nanoporous Platinum

Bang¹,

Han

Shin

et al. 2021

ChemElectroChem

View full text Add to dashboard Cite

Nanoporous electrodes are representative electrode materials for diverse applications, such as energy conversion devices and sensors. Recently, selectivity based on the size of ions arising from nanoporous structures has been applied to capacitive deionization, electrochemical supercapacitors, and conductometry. Herein, we explored the selectivity based on the size of the redox molecules on the electrochemical reaction at the nanoporous Pt electrode with extremely small (1-2 nm) and uniform pores by linear sweep voltammetry and AC impedance spectroscopy. Among primary alcohols with sizes smaller than that of the pores, we observed exceptional selective enhancement in the case of methanol due to its smallest size, despite all the alcohols having a similar reaction mechanism. These findings may provide an insight into electrochemical analysis and electrocatalysis based on nanoporous structures.Devices based on electrochemical principles, such as energyconversion devices (for example, batteries, supercapacitors, fuel cells, and solar cells) and chemical/bio sensors are ubiquitous. The performance of these devices depends on the properties of the electrodes. Rapid advances in nanoscience and nanotechnology have led to an increased interest in nanoscale electrochemistry to improve the performance of these devices. Recently, nanoporous electrodes have been extensively utilized in the fields of energy conversion, sensors, and catalysts owing to their high surface-to-volume ratio. [1] More recently, the effect

show abstract

“…Shermukhamedov et al used the electron transfer theory and classical molecular dynamics simulations to make qualitative predictions of electron transfer in aqueous solutions inside nanochannels. 46 The total reorganization energy  in the reaction process was estimated:…”

Section: Mechanisms and Theory Of Cce Within Nanochannelsmentioning

confidence: 99%