Time-Resolved Laser-Induced Fluorescence Study of Photoinduced Electron Transfer at the Water/1,2-Dichloroethane Interface

Dryfe, Robert A. W.; Ding, Zhifeng; Wellington, R. Geoffrey; Brevet, Pierre F.; Kuznetzov, and Alexander M.; Girault, Hubert H.

doi:10.1021/jp9630434

Cited by 25 publications

(19 citation statements)

References 18 publications

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“…Among other methods to study the ET phenomena at the ITIES, such as scanning electrochemical microscopy (SECM), 31 an electron-conductor separated oil-water system (ECSOW) 32 or in situ uorescence spectroscopy, 33 Fermin et al…”

Section: 2930mentioning

confidence: 99%

Electrovariable gold nanoparticle films at liquid–liquid interfaces: from redox electrocatalysis to Marangoni-shutters

et al. 2017

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Control over the physical properties of nanoparticle assemblies at a liquid-liquid interface is a key technological advancement to realize the dream of smart electrovariable nanosystems.Electrified interfaces, such as the interface between two immiscible electrolytes solutions (ITIES), are almost an ideal platform for realizing this dream. Here, we show that the Galvani potential difference across soft interfaces can be effectively used to manipulate: (i) the reactivity of gold nanoparticle assemblies through varying the Fermi level (both chemically and electrochemically); (ii) the location distribution of the nanoparticles at the liquid-liquid interface. In the first case, in addition to our previous studies on electron transfer reactions (ET) across the ITIES, we used intensity modulated photocurrent spectroscopy (IMPS) to study the kinetics of photo-induced electrochemical reactions at the ITIES. As expected, the direct adsorption of gold nanoparticles at the interface modifies the kinetics of the ET reaction (socalled, interfacial redox electrocatalysis), however it did not lead to an increased photocurrent by "plasmonic enhancement". Rather, we found that the product separation depends on double layer effects while the product recombination is controlled by the Galvani potential difference between the two phases. In the second case, we demonstrated that polarizing the ITIES caused migration of gold nanoparticles from the middle region of the cell to its periphery. We called such systems "Marangoni-type shutters". This type of electrovariable plasmonic system did not experience diffusion limitation in terms of the adsorption/ desorption of nanoparticles and the entire movement of nanoparticle assemblies happened almost instantly (within a second). It opens a fresh view on electrovariable plasmonics and presents new opportunities to create smart nanosystems at the ITIES driven with an electric field.

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Section: 2930mentioning

confidence: 99%

Electrovariable gold nanoparticle films at liquid–liquid interfaces: from redox electrocatalysis to Marangoni-shutters

et al. 2017

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“…Combining Eqs. (17) and (20), the following expression is obtained for the electric current density:…”

Section: Model a -First Order Back Electron Transfermentioning

confidence: 99%

“…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%

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

Samec

Eugster

Fermı́n

2005

Journal of Electroanalytical Chemistry

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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.

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“…This includes scanning electrochemical microscopy (SECM), [15][16][17][18][19][20][21][22][23][24][25][26] thin-layer cyclic voltammetry, [27][28] and spectro-electrochemical methods (some utilizing recent advances in non-linear optics). [5][6][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] 3…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

Cooper

Benjamin

2014

J. Phys. Chem. B

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Abstract:Several aspects of the photoinduced electron transfer (ET) reaction between coumarin 314 (C314) and N,N-dimethylaniline (DMA) at the water/DMA interface are investigated by molecular dynamics simulations. New DMA and water/DMA potential energy surfaces are developed and used to characterize the neat water/DMA interface.The adsorption free energy, the rotational dynamics and the solvation dynamics of C314 at the liquid/liquid interface are investigated and are generally in reasonable agreement with available experimental data. The solvent free energy curves for the ET reaction between excited C314 and DMA molecules are calculated and compared with those calculated for a simple point charge model of the solute. It is found that the reorganization free energy is very small when the full molecular description of the solute is taken into account. An estimate of the ET rate constant is in reasonable agreement with experiment. Our calculations suggest that the polarity of the surface "reported" by the solute, as reflected by solvation dynamics and the reorganization free energy, is strongly solute-dependent.

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Time-Resolved Laser-Induced Fluorescence Study of Photoinduced Electron Transfer at the Water/1,2-Dichloroethane Interface

Cited by 25 publications

References 18 publications

Electrovariable gold nanoparticle films at liquid–liquid interfaces: from redox electrocatalysis to Marangoni-shutters

Electrovariable gold nanoparticle films at liquid–liquid interfaces: from redox electrocatalysis to Marangoni-shutters

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

Photoinduced Excited State Electron Transfer at Liquid/Liquid Interfaces

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