Studies in photoelectrochemistry:  a theoretical model for induced charging currents in potentiostatic chronoamperometry

Fratoni, S. S.; Perone, S. P.

doi:10.1021/ac60366a001

Cited by 39 publications

(37 citation statements)

References 36 publications

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“…(13)(14)(15)(16) Theoretical studies have also been initiated both with respect to the kinetics of scavenging itself (17_-18) and transient effects in the electrochemical detection of the photorelated phenomena. (21) Many previous experimental studies have been carried out with continuous or chopped radiaion sources, monitoring the steady state (DC) (22) or modulated(4«9.15,23) photocurrents under potentiostatic conditions. Most of the more recent work has used pulsed xenon flashlamps.…”

Section: Photoemission Of Electrons From Mercury Electrodes Into Elecmentioning

confidence: 99%

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Laser Applications in Photoelectrochemistry

Perone

Richardson

Shepard

et al. 1978

ACS Symposium Series

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Photoemission Studies. The UV-visible irradiation of an electrode/solution interface can stimulate any of several interesting electrode processes. If the solution does not absorb and the electrode is a metallic conductor, photoemission of electrons may occur, with the formation of solvated electrons and initiation of reactions with available scavengers. If the solution absorbs the radiation and photolysis occurs, electroactive photolytic intermediates and products may be detected at an indicator electrode by their electrolysis currents under potentiostatic conditions. If the electrode is a semiconductor and absorbs radiation sufficient to promote electrons through the band gap, oxidation or reduction process may be induced which would not occur in the absence of radiation.If a dye absorbed on a semiconductor electrode is excited by the irradiation, the excited state may undergo an oxidative or reductive electron transfer step which would not occur with the ground state species.These are examples of some of the more interesting radiation-induced electrode processes which have been studied. Much of the interest has been stimulated recently by the prospects for direct solar-to-electrical energy or solar-to-chemical energy conversion which might be possible with photoelectrochemical ce lis.(1-3) The work reported here was designed to demonstrate the utility of laser sources for these photoelectrochemical studies; we have focused our attention on those phenomena uniquely related to the characteristics of laser irradiation.In particular, we report here the results of our studies of laser-induced photoemission processes and laser -induced photolysis. The former study was undertaken to illustrate the efforts of wavelength, source power, and intensity on photoemission-related process; whereas the latter study was designed to illustrate the capabilities for photoelectrochemical quantum yield measurements on transient photolytic species made possible with a laser source.

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Section: Photoemission Of Electrons From Mercury Electrodes Into Elecmentioning

confidence: 99%

“…21 Procedures for Laser Photolysis Studies. The temperatures of the laser dye and the water surrounding the triax adapter were initially equilibrated to + 0.1°C.…”

Section: In the Present Experiments The Transient Current Signal Was mentioning

confidence: 99%

Laser Applications in Photoelectrochemistry

Perone

Richardson

Shepard

et al. 1978

ACS Symposium Series

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“…[1] and rearranging gives This general expression is next modified to represent the npecific conditions present during the measurement.…”

Section: Theorymentioning

confidence: 99%

“…For this work, flash-initiated electrolysis currents will be assumed, with a typical example of the electrode process h~ O , > R [3] R--> 0 -k he- [4] Previously (1,4), the specific case where R was a stable species, and reaction [4] produced dii~usion-lim~ted faradaic currents described by the Cottrell equation, was considered. The results indicated that, rather than following the expected Cottrell behavior, the measured current should reflect both charging and faradaic contributions, as described by Eq.…”

Section: It(s) = ~ 1 S + --~-mentioning

confidence: 99%

“…Even under applied potentiostatic conditions, such as in flash photoelectrochemical studies (2,3), changing faradaic current causes a change in potential across the double layer and consequently induces charging current to flow. Thus, a theoretical model was developed (1) to characterize this effect. Thus, a theoretical model was developed (1) to characterize this effect.…”

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Studies in Photoelectrochemistry: III . Theory for Induced Charging Currents in Potentiostatic Chronoamperometry Involving Competing Chemical Reactions

Fratoni¹,

Perone²

1976

J. Electrochem. Soc.

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The first paper in this series (i) developed a theoretical model for characterizing the charging currents induced by changing faradaic currents measured under potentiostatic conditions. This paper describes application of the theoretical model to measurements involving electrolysis mechanisms complicated by competing reactions. The model is particularly relevant for flash photoelectrochemical studies. The mechanisms considered here include first order and second order decay of electroactive photoproducts. The dependence of measured currents on various experimental and chemical parameters--including the cell time-constant, photoproduct concentrations, and rate constants--is described for a wide range of conditions. Theoretical relationships can be used to predict total measured currents, or to tabulate correction factors to extract purely faradaic currents from measured currents. In addition, an alternative derivative-correction method for extracting faradaie signals from combined currents is described.

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Electrochemical preparation of semipermeable polymer membranes on carbon fiber microelectrodes for selective amperometric detection of cations

Potje‐Kamloth

Josowicz

1992

Ber Bunsenges Phys Chem

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An electrochemical procedure is presented for in situ preparation and subsequent deposition of semipermeable membranes on ultramicroelectrodes. The membranes are based on a matrix of poly(oxyphenylene) bearing carboxyl and sulfonic groups, i.e. poly(1,2‐oxyphenylene‐4‐sulfonic acid) or poly(1,2‐oxyphenylene‐3‐carboxylic acid). These membranes exhibit a cation exchange behavior whereas the transport of anions is inhibited. The diffusion coefficients of Ru(NH3)6·3+ within the semipermeable membranes could be estimated by means of chronoamperometric and steady‐state measurements. The values obtained are in the range of 1.0–6.9 · 10−7 cm2/s. The permeability of the cation through the membranes is high. Therefore, no distortion of the voltammetric response due to the attached membrane is observed. It is shown that the transport rate can be modulated by copolymerization of the functionalized phenolic monomer with varying amounts of a cross‐linking agent. The ultramicroelectrodes modified with the above membranes can be used as amperometric sensors displaying a linear current/concentration relationship.

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Studies in photoelectrochemistry: a theoretical model for induced charging currents in potentiostatic chronoamperometry

Cited by 39 publications

References 36 publications

Laser Applications in Photoelectrochemistry

Laser Applications in Photoelectrochemistry

Studies in Photoelectrochemistry: III . Theory for Induced Charging Currents in Potentiostatic Chronoamperometry Involving Competing Chemical Reactions

Electrochemical preparation of semipermeable polymer membranes on carbon fiber microelectrodes for selective amperometric detection of cations

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