Electrochromic Changes of Light Absorption by the Electric Field of the Electrolytic Double Layer

Plieth, W.; Gruschinske, P.; Hensel, H.-J.

doi:10.1002/bbpc.197800128

Cited by 28 publications

(12 citation statements)

References 14 publications

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“…Instead of measuring an electrical signal (e.g., current and charge), one could also study electrochemical reactions via optical detection . Studies have found that electrochemical reactions are accompanies by changes in optical properties, such as reflectivity of an electrode. − However, the reflectivity changes are often small. To amplify the optical signal, an interferometric method has been used to study electrochemical reactions via detecting changes in the refractive index in the electrolyte. − The interferometric method measures both changes on the electrode surface and in the electrolyte, which cannot be easily deconvoluted.…”

Section: Introductionmentioning

confidence: 99%

Plasmonic Imaging of Electrochemical Reactions of Single Nanoparticles

Fang

Wang

et al. 2016

Acc. Chem. Res.

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Electrochemical reactions are involved in many natural phenomena, and are responsible for various applications, including energy conversion and storage, material processing and protection, and chemical detection and analysis. An electrochemical reaction is accompanied by electron transfer between a chemical species and an electrode. For this reason, it has been studied by measuring current, charge, or related electrical quantities. This approach has led to the development of various electrochemical methods, which have played an essential role in the understanding and applications of electrochemistry. While powerful, most of the traditional methods lack spatial and temporal resolutions desired for studying heterogeneous electrochemical reactions on electrode surfaces and in nanoscale materials. To overcome the limitations, scanning probe microscopes have been invented to map local electrochemical reactions with nanometer resolution. Examples include the scanning electrochemical microscope and scanning electrochemical cell microscope, which directly image local electrochemical reaction current using a scanning electrode or pipet. The use of a scanning probe in these microscopes provides high spatial resolution, but at the expense of temporal resolution and throughput. This Account discusses an alternative approach to study electrochemical reactions. Instead of measuring electron transfer electrically, it detects the accompanying changes in the reactant and product concentrations on the electrode surface optically via surface plasmon resonance (SPR). SPR is highly surface sensitive, and it provides quantitative information on the surface concentrations of reactants and products vs time and electrode potential, from which local reaction kinetics can be analyzed and quantified. The plasmonic approach allows imaging of local electrochemical reactions with high temporal resolution and sensitivity, making it attractive for studying electrochemical reactions in biological systems and nanoscale materials with high throughput. The plasmonic approach has two imaging modes: electrochemical current imaging and interfacial impedance imaging. The former images local electrochemical current associated with electrochemical reactions (faradic current), and the latter maps local interfacial impedance, including nonfaradic contributions (e.g., double layer charging). The plasmonic imaging technique can perform voltammetry (cyclic or square wave) in an analogous manner to the traditional electrochemical methods. It can also be integrated with bright field, dark field, and fluorescence imaging capabilities in one optical setup to provide additional capabilities. To date the plasmonic imaging technique has found various applications, including mapping of heterogeneous surface reactions, analysis of trace substances, detection of catalytic reactions, and measurement of graphene quantum capacitance. The plasmonic and other emerging optical imaging techniques (e.g., dark field and fluorescence microscopy), together with the scanning probe-...

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Section: Introductionmentioning

confidence: 99%

Plasmonic Imaging of Electrochemical Reactions of Single Nanoparticles

Fang

Wang

et al. 2016

Acc. Chem. Res.

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“…The potential modulated ER spectrum due to an adsorbate molecule could also originate from direct charge-electric field interaction (electrochromism). This type of response is usually obtained at electrode potentials that are far from the redox value, and has a shape corresponding to the first derivative of the absorption spectrum of the adsorbate (23,27). The characteristics of the ER spectra reported in this work suggest that they are not related to electrochromism.…”

Section: Resultsmentioning

confidence: 76%

“…For our detection sensitivity (DR/R Ç 10 06 ), it is feasible to follow these The differential reflectance measures the difference in reflection between the case when a protein layer is present on charge transfer reactions even at submonolayer quantities of Pdx adsorbate since the difference in the absorption spectra between the two redox forms, Pdx ox and Pdx red , is substantial. Similar optical detection of faradaic transitions has been reported recently for adsorbed organic dyes (22)(23)(24)(25), metal porphyrins (27), and heme proteins (10,11,26).…”

Section: Optical Foundations Of Electroreflection Measurementmentioning

confidence: 64%

Observation of Electron Transfer between a Silver Electrode and Putidaredoxin Using Electromodulated Reflectance Spectroscopy

Gaigalas

Reipa

Vilker

1997

Journal of Colloid and Interface Science

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“…Consequently, the band shift effect seems to be absent in the optical response of the adsorbed methylene blue. According to the theory derived by Liptay [25] and Plieth et al [26], the band shift effect can be expressed by equations as follows: ENERGY,,.= (I/J;] -]p./()(cos +)F+ ENERGY,=,…”

Section: High Coveragementioning

confidence: 99%

“…A linear dependence of the wave function and the transition moment on the field strength is predicted by first-order perturbation theory. The analysis of this effect applied to the electrochemical interphase leads to relationships that depend linearly on either the modulation amplitude or both the modulation amplitude and the bias potential [26].…”

Section: F=f+b(e-e+) (3)mentioning

confidence: 99%

In-situ spectroelectrochemistry of adsorbed methylene blue on a sulphur-modified gold electrode

Lezna¹,

Hahn²,

Arvía³

1991

Journal of Electroanalytical Chemistry and Interfacial Electroc

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The properties of a methylene blue layer adsorbed onto a sulphur-modified gold electrode have been studied by electrochemical and in-situ reflectance spectroscopy in the visible region. At saturation coverage, methylene blue monomer and dimer bands were observed in the double-layer region through the electrochromism of the adsorbed film arising from the effect of the double-layer field on the molecule transition moment. Possible dye orientations in the adsorbed state are discussed with the aid of the optical measurements.At low surface concentrations, the optical signal stems from modulation of the monomer/dimer interconversion.Repeated electrochemical reduction and oxidation of adsorbed methylene blue result in gradual desorption of the dimer species, probably due to a change in the molecular geometry upon reduction which may evolve from a planar configuration to a folded structure.

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Electrochromic Changes of Light Absorption by the Electric Field of the Electrolytic Double Layer

Cited by 28 publications

References 14 publications

Plasmonic Imaging of Electrochemical Reactions of Single Nanoparticles

Plasmonic Imaging of Electrochemical Reactions of Single Nanoparticles

Observation of Electron Transfer between a Silver Electrode and Putidaredoxin Using Electromodulated Reflectance Spectroscopy

In-situ spectroelectrochemistry of adsorbed methylene blue on a sulphur-modified gold electrode

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