Electrochemical formation and deposition of polyaniline on electrode surface; In situ raman spectroscopical study

Efremova, Anastasiia; Régis, A.; Arsov, Ljubomir

doi:10.1016/0013-4686(94)80033-2

Cited by 38 publications

(15 citation statements)

References 17 publications

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“…In the 350-900 cm 1 range, on increasing the concentration of H 2 SO 4 , the SERS spectra show for the rough Ag and Au supports a decrease in intensity of the bands at 400 and 515 cm 1 and a growth in intensity of the band at 585 cm 1 , bands associated with semiquinoid and quinoid ring in-plane deformation. 12 In the final doping state corresponding to high acid concentrations, the SERS spectra are identical with those that were obtained on polyaniline-emeraldine salt synthesized by cyclic voltammetry in an acid medium. 13 (iii) As the degree of HSO 4 ion doping is increased, the SERS spectra show changes in the profile and maximum position of the band attributed to C-H bending Q 1162 cm 1 .…”

Section: Polymer-metallic Support Interface Reactions Evidenced By Sesupporting

confidence: 62%

Interfacial chemical effect evidenced on SERS spectra of polyaniline thin films deposited on rough metallic supports

Baibarac

Mihuţ

Louarn

et al. 1999

J. Raman Spectrosc.

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Surface-enhanced Raman scattering (SERS) has proved to be an effective technique for studying the structural properties of conducting polymer thin films. The enhancement process has a twofold origin, electromagnetic and chemical. The electromagnetic enhancement, which is the dominant mechanism in SERS generation, consists in the excitation of localized and delocalized surface plasmons (SPs) in the metallic support of the thin film. The Raman emission of the adsorbed molecules on the metal surface (the most efficient being Ag, Au and Cu) is due to the intense evanescent electromagnetic field located at the interface between the metal and the surrounding medium. The second enhancing mechanism for SERS is of chemical origin, involving the formation of new chemical bonds between the molecules and the metal surface, with the polarizability thus becoming considerably higher than that of the free molecules. This mechanism is as a rule accompanied by a metal-molecule or molecule-metal charge transfer, which partly accounts for the success of the SERS studies on conducting polymers. Unfortunately, these studies have revealed that the chemical effects at the polymer-metal interface varied substantially depending on the various types of polymer and metallic support. In this context, polyaniline containing two different entities (a reduced and an oxidized state) in its repeating units exhibits specific alterations in its SERS spectra depending on the type of metallic support. This paper presents new results concerning the structure of emeraldine-base and emeraldine-salt polyaniline thin films deposited on rough Ag and Au supports. The effect on the SERS spectra of the polymer-metal and polymer-ambient interface chemical reactions is also described. The presence of an interface compound depending on the oxidizing properties of the metallic support has a strong influence on the SERS spectra, no matter how the PAN films were deposited on the support (whether by solvent evaporation or by an electrochemical process, i.e. cyclic voltammetry). When an emeraldine base is doped with HSO 4 − ions, it turns into an emeraldine salt, which exhibits a disordered state in its macromolecular chain, leading to a modified profile of the ∼1162 cm −1 Raman line which is associated with the C-H bond of the quinoid ring. The Lorentzian profile is altered by the addition of a Gaussian profile component. For a rough Ag support, the SERS spectra show that the transformation of emeraldine base films into emeraldine salt films is a reversible process.

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Section: Polymer-metallic Support Interface Reactions Evidenced By Sesupporting

confidence: 62%

Interfacial chemical effect evidenced on SERS spectra of polyaniline thin films deposited on rough metallic supports

Baibarac

Mihuţ

Louarn

et al. 1999

J. Raman Spectrosc.

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“…1 shows Raman spectra of polyaniline (PANI) layer at a gold electrode in pH 1.0 and pH 7.0 solutions. The bands observed could be assigned based on the known data [14][15][16][17][18][19]. Generally, most characteristic vibrations could be divided into three spectral regions.…”

Section: Methodsmentioning

confidence: 99%

Raman spectroelectrochemical study on the kinetics of electrochemical degradation of polyaniline

Mažeikienė

Niaura

Malinauskas

2008

Polymer Degradation and Stability

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“…Typical CV behavior.-Type I PANI films were electrodeposited using the most typical conditions used in the literature, i.e., by cycling the potential at 100 mV s Ϫ1 between 0 and approximately 1 V. 26 Films were grown to various thicknesses, and subsequent impedance studies focused on three particular films, which were 55, 80, and 215 nm thick. Figure 1 shows the CV responses for five films formed on Au in the aniline/sulfuric acid growth solution.…”

Section: Type I Pani Films Deposited On Au Electrodesmentioning

confidence: 99%

The Effect of Film Thickness and Growth Method on Polyaniline Film Properties

Dinh

Vanýsek

Birss

1999

J. Electrochem. Soc.

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There has been significant interest in the electrochemical properties of polyaniline (PANI) films on electrode surfaces, largely because of the many promising applications of PANI in electrochromic devices, 1,2 as supercapacitive materials, as intercalating electrodes in advanced batteries, 3,4 for electrocatalysis of certain reactions, [5][6][7] in microelectronic devices, 8 etc.The properties of PANI films have been extensively studied by many different methods. However, despite the numerous past studies of PANI films, there are still many remaining questions regarding their electrochemical growth mechanism, their structure (particularly at the nanometer scale), and even their electrical properties. Although the impedance technique has been employed quite frequently as a tool for investigating PANI film properties, 9-17 many of these past studies have focused on the characterization of a single film at different potentials, or of several films of different thickness, but grown by one technique. No single study has been directed at comparing the electrochemical properties of PANI films formed at different rates to different thicknesses at different substrates, etc. As a consequence, there is some uncertainty regarding the dependence of film properties on experimental variables. In fact, many past studies have focused more on the description of the impedance data without much emphasis on interpretation.Therefore, one of the key objectives of this work was to examine the PANI film impedance response over a wide range of potentials for films formed to various thicknesses while employing several different electrochemical growth conditions on Au and Pt substrates. The principal goal of these studies has been to obtain a better understanding of the growth and structural properties of these films from a careful variation of the experimental parameters within a single controlled study.In this paper, the electrochemical properties of PANI films, grown by two different methods (type I and type II films) to various thicknesses and studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), are examined systematically. The structural and interfacial properties of the two types of films are compared, for the first time, by tracking the rate of the hydrogen evolution reaction (HER) with time of PANI film growth. It is shown that type II films are more porous, both in the bulk of the film and at the base of film pores, and are more capacitive than type I films. Type II films also undergo structural changes during film growth, while type I films remain relatively uniform. This work is considered important in terms of providing knowledge regarding how the growth parameters affect PANI film properties and also insight into how to design PANI films with the desired structure, porosity, capacitance, and stability characteristics. ExperimentalCells and electrodes.-The details of the solutions and the instrumentation used for carrying out CV and ac impedance measurements have been described elsewhere. 18 Sta...

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Electrochemical formation and deposition of polyaniline on electrode surface; In situ raman spectroscopical study

Cited by 38 publications

References 17 publications

Interfacial chemical effect evidenced on SERS spectra of polyaniline thin films deposited on rough metallic supports

Interfacial chemical effect evidenced on SERS spectra of polyaniline thin films deposited on rough metallic supports

Raman spectroelectrochemical study on the kinetics of electrochemical degradation of polyaniline

The Effect of Film Thickness and Growth Method on Polyaniline Film Properties

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