Evidence for adsorption of Fe(CN)63−/4− on gold using the indirect laser-induced temperature-jump method

Smalley, John F.; Geng, Lin; Feldberg, Stephen W.; Rogers, Lee C.; Leddy, Johna

doi:10.1016/0022-0728(93)80520-r

Cited by 45 publications

(63 citation statements)

References 20 publications

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“…Also the temperature dependence of the heterogeneous electron transfer process [9] and the kinetics of complex electrochemical processes such as oxygen reduction on platinum [10] have been studied. Methods based on laser pulse heating [11] and thermal modulation [12] have been described. Extensive tables of thermodynamic data describing the effect of temperature on equilibrium potentials are available [13,14].…”

Section: Introductionmentioning

confidence: 99%

Microwave Activated Voltammetry: The Thermally Enhanced Anodic Stripping Detection of Cadmium

et al. 2000

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In situ microwave activation of electrochemical processes in a novel electrochemical cell, in which intense microwave radiation is focused locally into the region at the electrode surface±solution interface, is shown to allow high-temperature voltammetry experiments at 100 mm Pt disk electrodes. Factors such as the cell geometry and the deposition of a thin ®lm of mercury are shown to in¯uence the microwave effect. The detection of trace metals or impurities by anodic stripping voltammetry is a routinely applied procedure with applications especially in rapid online monitoring, in remote place analysis, or for extremely dilute samples. For cadmium detection by anodic stripping voltammetry microwave radiation is demonstrated to strongly affect the accumulation process but not the stripping process. Calibration of the effects induced by microwave radiation on the experimentally observed voltammetric data, based on the equilibrium potentials for the FeCN 4Àa3À 6 and the RuNH 3 3a2 6 redox systems, demonstrates that the data obtained are consistent with a thermally enhanced process. The temperature achievable at the electrode±solution interface before boiling and cavitation occurs, is shown to be strongly dependent on the type of electrode material and surface morphology. At a mercury ®lm electrode deposited on platinum temperatures in excess of 150C can be applied in voltammetric experiments in a constant heating mode.

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Section: Introductionmentioning

confidence: 99%

Microwave Activated Voltammetry: The Thermally Enhanced Anodic Stripping Detection of Cadmium

et al. 2000

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“…4 of Ref. [5]. This transient demonstrates that the ILIT response for an electrolyte solution containing just KF is a function of DT(t) alone (i.e., no interfacial charge-transfer is evident).…”

Section: Discussionmentioning

confidence: 85%

“…This transient demonstrates that the ILIT response for an electrolyte solution containing just KF is a function of DT(t) alone (i.e., no interfacial charge-transfer is evident). 5 The ILIT transient shown in Fig. 1 describes the open-circuit potential change effected by a time-dependent (ILIT) temperature change [5].…”

Section: Discussionmentioning

confidence: 99%

“…Nevertheless, because the size of the open-circuit response of an electrode-electrolyte interface to an ILIT temperature perturbation is sensitive to the presence of ions adsorbed on the surface of the electrode [1,[4][5][6][7][8], the ILIT technique can also be used to measure [8] the kinetics of fast, ion adsorption/desorption reactions [9,10]. These reactions are relevant [9] to a large number of technologically important electrochemical processes such as the hydrogen oxidation [9,11] 1 and the oxygen reduction [9,17] reactions in hydrogen fuel cells.…”

Section: Introductionmentioning

confidence: 99%

“…(36), C cm À2 Dq ad,inj (t) see Eq. solution-dissolved redox couple [4,5] if only the adsorbed species undergo electron-transfer.…”

Section: Introductionmentioning

confidence: 99%

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

Smalley¹

2010

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Mass transfer to a nanoelectrocatalyst

Robinson,

Jordan,

Wiesner

2024

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There are few studies of mass transfer to nanospheres (1 nm ≤ dp ≤ 100 nm). We have experimentally investigated the electrocatalytic reduction of hexacyanoferrate (III) to hexacyanoferrate (II) on gold nanospheres. The surface flux is insensitive to particle sizes of dp ≥ 30 nm and is essentially identical to that for a diffusion‐limited system. However, the measured fluxes in the range 5 nm ≤ dp ≤ 30 nm were one to three orders of magnitude smaller than predicted by a purely diffusion‐limited model. Using mathematical modeling, we evaluated six mechanisms affecting mass transfer to a nanoparticle in our experimental system. Among potential acceleratory effects, the curvature effect sharply increased the surface flux by a factor of 20. Other acceleratory effects of Brownian advection and enhanced surface reactivity played negligible roles, the latter due to screening by a charged stabilizing layer. Deceleratory effects of increased tortuosity by stabilizing layers and particle aggregation also played negligible roles. Electrostatic repulsion dominated mass transfer for dp ≤ 30 nm. This finding suggests tuning the charge and the tortuosity of the stabilizer layer to potentiate the flux will be useful in engineering nanosuspensions.

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Evidence for adsorption of Fe(CN)63−/4− on gold using the indirect laser-induced temperature-jump method

Cited by 45 publications

References 20 publications

Microwave Activated Voltammetry: The Thermally Enhanced Anodic Stripping Detection of Cadmium

Microwave Activated Voltammetry: The Thermally Enhanced Anodic Stripping Detection of Cadmium

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

Mass transfer to a nanoelectrocatalyst

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