Kinetics of interfacial ion-transfer reactions studied using the indirect laser-induced temperature jump technique: Theory

Smalley, John F.

doi:10.1016/j.jelechem.2010.01.003

Cited by 6 publications

(6 citation statements)

References 22 publications

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“…The kinetics of ET between the electrode and a redox-active moiety through SAM can be monitored by electrochemical, photochemical, and temperature jump techniques. 5,15,24,25 Among the various electrochemical methods available, cyclic voltammetry (CV) and chronoamperometry (CA) have been widely used to study the ET kinetics across the SAM. 1,26,27 The high-resolution crystal structure and the quantification of H 2 gas produced during SAM formation indicate that the Au− thiol interface in SAM-coated nanoparticles contains thiolates.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The kinetics of ET between the electrode and a redox-active moiety through SAM can be monitored by electrochemical, photochemical, and temperature jump techniques. ,,, Among the various electrochemical methods available, cyclic voltammetry (CV) and chronoamperometry (CA) have been widely used to study the ET kinetics across the SAM. ,, The high-resolution crystal structure and the quantification of H 2 gas produced during SAM formation indicate that the Au–thiol interface in SAM-coated nanoparticles contains thiolates. − On the other hand, the adsorption of thiol on the Au(111) electrode can proceed either via dissociative pathways (−SH scission) or non-dissociative pathways (−SH intact) . During the study of the pathways of adsorption of methanethiol on Au(111) by density functional theory, Lustemberg et al have found that CH 3 S and dissociated H adsorb at the bridging and hollow sites, respectively .…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Isotope Effects on Electron Transfer Across Self-Assembled Monolayers on Gold

2021

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Reactions requiring controlled delivery of protons and electrons are important in storage of energy in small molecules. While control over proton transfer can be achieved by installing appropriate chemical functionality in the catalyst, control of electron-transfer (ET) rates can be achieved by utilizing self-assembled monolayers (SAMs) on electrodes. Thus, a deeper understanding of the ET through SAM to an immobilized or covalently attached redox-active species is desirable. Long-range ET across several SAM-covered Au electrodes to covalently attached ferrocene is investigated using protonated and deuterated thiols (R–SH/R–SD). The rate of tunneling is measured using both chronoamperometry and cyclic voltammetry, and it shows a prominent kinetic isotope effect (KIE). The KIE is ∼2 (normal) for medium-chain-length thiols but ∼0.47 (inverse) for long-chain thiols. These results imply substantial contribution from the classical modes at the Au–(H)SR interface, which shifts substantially upon deuteration of the thiols, to the ET process. The underlying H/D KIE of these exchangeable thiol protons should be considered when analyzing solvent isotope effects in catalysis utilizing SAM.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Kinetic Isotope Effects on Electron Transfer Across Self-Assembled Monolayers on Gold

2021

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“…13 The kinetics of ET between the electrode and a redox active moiety through SAM can be monitored by electrochemical, photochemical and temperature jump techniques. 4,11,[14][15] Among various electrochemical methods available, cyclic voltammetry and chronoamperometry have been widely used to study the ET kinetics across the SAM. 1,[16][17] The structure of Au-thiol interfaces in thiol coated nanoparticles (3D SAMs) and thiol SAM on Au surfaces (2D SAMs) are different.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Isotope Effect on Electron Transfer Rates Across Self-Assembled Monolayers: A Case for Quantum Effects

Chattopadhyay¹,

Bandyopadhyay²,

Dey³

2019

Preprint

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Long range ET across several self-assembled mon-olayer (SAM) covered Au electrodes is investigated using protonated and deuterated thiols (RSH/RSD). The rate of tunneling is measured using both chronoamperometry and cyclic voltammetry and it shows a prominent KIE. The KIE is ~2 (normal) for medium chain length thiols where the Tafel plot indicate substantial through space tunneling and is ~0.25 (inverse) for long chain thiols where the Tafel plot indicate mostly through bond tunneling. These results imply substantial contribution from the classical modes at the Au-(H)SR interface, which shift substantially on deuteration of the thiols, to the ET process.<br>

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“…[1][2][3] According to a recent development of experimental methods, the dynamics has been revealed at the molecular-level. [4][5][6][7][8][9][10][11][12][13][14][15][16] For example, McGuire and Shen investigated vibrational dynamics of water near the interface of silica with time-resolved sum-frequency vibrational spectroscopy. 11 Yamakata and Osawa investigated the dynamics of water molecules on CO-covered Pt electrode using laser-induced temperature jump method.…”

Section: Introductionmentioning

confidence: 99%

A theory for time-dependent solvation structure near solid-liquid interface

Iida

Sato

2012

The Journal of Chemical Physics

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We propose a theory to describe time-dependent solvation structure near solid-liquid interface. Recently, we have developed two-dimensional-reference interaction site model to describe solvation structure near solid-liquid interface at the equilibrium state. In the present study, the theory is extended to treat dynamical aspect of the solvation; site-site Smoluchowski-Vlasov equation and surrogate Hamiltonian description are utilized to deal with the time-dependency. This combination enables us to access a long-time behavior of solvation dynamics. We apply the theory to a model system consisting of an atomistic wall and water solvent, and discuss the hydration structure dynamics near the interface at the molecular-level.

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Kinetics of interfacial ion-transfer reactions studied using the indirect laser-induced temperature jump technique: Theory

Cited by 6 publications

References 22 publications

Kinetic Isotope Effects on Electron Transfer Across Self-Assembled Monolayers on Gold

Kinetic Isotope Effects on Electron Transfer Across Self-Assembled Monolayers on Gold

Kinetic Isotope Effect on Electron Transfer Rates Across Self-Assembled Monolayers: A Case for Quantum Effects

A theory for time-dependent solvation structure near solid-liquid interface

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