Heterogeneous electron transfer reactions at liquid/liquid interfaces studied by time-resolved absorption spectroscopy

Duong, H. Dung; Brevet, Pierre F.; Girault, Hubert H.

doi:10.1016/s1010-6030(98)00316-5

Cited by 11 publications

(7 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The first measurements of photocurrent responses associated with heterogeneous photoinduced electron transfer were published by Marecek et al [8] for the reduction of methylviologen in the aqueous phase by RuðbpyÞ 2þ 3 in DCE or benzonitrile under chopped illumination. Although this work raised criticism due to the apparent absence of dc photocurrents under constant illumination [9], it opened the way to studies providing clear evidence of photoinduced electron transfer employing photocurrent measurements [10][11][12][13][14] or spectroscopic techniques [15][16][17][18]. During the last five years, efforts have been devoted to the exploration of fundamental aspects concerning the organisation and reactivity of photoactive species at the interface between two immiscible electrolyte solutions [15,19,20].…”

Section: Introductionmentioning

confidence: 99%

“…During the last five years, efforts have been devoted to the exploration of fundamental aspects concerning the organisation and reactivity of photoactive species at the interface between two immiscible electrolyte solutions [15,19,20]. In these systems, the photoexcitation of dyes or semiconducting nanoparticles leads to heterogeneous charge transfer processes in the presence of redox couples located in the adjacent liquid phase [9,[12][13][14]18,[21][22][23][24][25][26][27]. These projects are relevant not only to theoretical aspects on electron transfer at molecular interfaces, but also to the development of new photoactive systems [9,22,28,29].…”

Section: Introductionmentioning

confidence: 99%

“…Recently, a series of papers based on photocurrent responses involving water soluble porphyrin species has addressed various aspects involved in the kinetics of photoinduced electron transfer across polarisable liquid| liquid junctions [12][13][14]18,[21][22][23][24][25][26][27]32]. A general description of the heterogeneous photoreaction is shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A generalised model for dynamic photocurrent responses at dye-sensitised liquid|liquid interfaces

Samec

Eugster

Fermı́n

2005

Journal of Electroanalytical Chemistry

Self Cite

View full text Add to dashboard Cite

The heterogeneous photoinduced electron transfer involving dyes adsorbed at the interface between two immiscible electrolyte solutions and redox molecules located in the adjacent phase manifests itself as photocurrent responses under potentiostatic conditions. Photocurrent transients as functions of the light intensity and bias potential allow the extraction of insightful information on the kinetics of the various processes associated with the photoinduced reaction. Previous analyses of this type of responses were based on phenomenological models that did not consider mass transport. In the present paper, we develop a generalised model for photocurrent transients taking into account the diffusion of reacting species to the interface. Comparison with the experimental data confirms that the responses can be described adequately by applying stationary conditions to the surface concentration of the photoactive species. Mechanistic aspects associated with the nature of the photocurrent relaxation on the microsecond time scale are examined. In particular, the dependence of the transient response on the light intensity indicates that charge recombination proceeds mainly as a first order reaction from an interfacial geminate ion pair. Coupled ion transfer reactions involving the photoproducts can also contribute to the photocurrent, depending on the formal ion transfer potential of the corresponding species.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A generalised model for dynamic photocurrent responses at dye-sensitised liquid|liquid interfaces

Samec

Eugster

Fermı́n

2005

Journal of Electroanalytical Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…Electrochemistry at ITIES is rather complicated, and bipolar electrochemistry is a very useful tool to test electrochemical systems that, subsequently, can be studied by LL electrochemistry. Although new spectroelectrochemical setups have been successfully developed for LL interfaces, − the improvement of bipolar setups has been limited to electrochemical and electrochemiluminescence studies. − Bipolar electrochemistry has been used significantly less than electrochemistry at the ITIES, but the development of new devices should be decisive for a number of applications. For these reasons, the main objective of this technical note is the combination of bipolar electrochemistry with different spectroscopic techniques using a simple, versatile, and functional spectroelectrochemical device.…”

mentioning

confidence: 99%

“…For these reasons, the main objective of this technical note is the combination of bipolar electrochemistry with different spectroscopic techniques using a simple, versatile, and functional spectroelectrochemical device. Spectroelectrochemistry is an effective way to obtain important information about the processes that occur at LL interfaces. − The selection of spectroscopic and electrochemical techniques among different spectral regions and multiple electrochemical procedures, respectively, depends on the system studied. , UV–vis absorption spectroscopy is perhaps the most used technique in spectroelectrochemistry and has been used for studying different types of chemical processes. − Developments in Raman spectroelectrochemistry have highlighted this technique as one of the best to characterize and study different materials and processes in many fields. − In the present work, most of the experiments were performed using UV–vis absorption spectroelectrochemistry, although Raman spectroelectrochemistry provided suitable information in the study of particular systems, as for example, carbon nanotubes.…”

mentioning

confidence: 99%

Bipolar Spectroelectrochemistry

2017

View full text Add to dashboard Cite

Bipolar electrochemistry is receiving growing attention in the last years, not only because it is an important tool for studying electron transfer processes, but also because it is really fruitful in the development of new analytical sensors. Bipolar electrodes show promising applications as a direct analytical tool since oxidation and reduction reactions take place simultaneously on different parts of a single conductor. There are several electrochemical devices that provide information about electron transfer between two immiscible electrolyte solutions, but to the best of our knowledge, this is the first time that a bipolar device is able to record two spectroelectrochemical responses concomitantly at two different compartments. It allows deconvolving the electrochemical signal into two different optical signals related to the electron transfer processes occurring at two compartments that are electrically in contact. The combination of an electrochemical and two spectroscopic responses is indeed very useful, providing essential advantages in the study of a huge variety of systems. The study of three different electrochemical systems, such as reversible redox couples, carbon nanotubes, and conducting polymers has allowed us to validate the new cell and to demonstrate the capabilities of this technique to obtain valuable time-resolved information related to the electron transfer processes.

show abstract

Liquid/Liquid Interfaces, Electrochemistry at

Reymond

Girault

2000

Encyclopedia of Analytical Chemistry

Self Cite

View full text Add to dashboard Cite

This article outlines the electrochemical methodology at the interface between two electrolyte solutions (ITIES). The fundamental concepts of the thermodynamics in biphasic systems are presented in order to show how ions are distributed between the two adjacent phases, and hence how a Galvani potential difference is established at an ITIES. Polarizable and nonpolarizable ITIES are then characterized, and it is further evidenced that the classical electroanalytical methodology at a solid electrode can be directly transposed to the ITIES, thereby allowing reversible charge‐transfer reactions to be easily monitored and interpreted. This theoretical approach is completed by a review of the analytical methods used at ITIES, namely cyclic voltammetry, dropping electrolyte electrodes, optical techniques and microinterfaces (which are the biphasic analogs of microelectrodes). The last part deals with the practical applications that electrochemistry at ITIES has attracted during the last decade in the development of amperometric ion sensors and detectors, in the extraction of metal ions by interfacial formation of a complex and in the assessment of the lipophilicity of ionizable drugs.

show abstract

Heterogeneous electron transfer reactions at liquid/liquid interfaces studied by time-resolved absorption spectroscopy

Cited by 11 publications

References 16 publications

A generalised model for dynamic photocurrent responses at dye-sensitised liquid|liquid interfaces

A generalised model for dynamic photocurrent responses at dye-sensitised liquid|liquid interfaces

Bipolar Spectroelectrochemistry

Liquid/Liquid Interfaces, Electrochemistry at

Contact Info

Product

Resources

About