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A UV-visible spectroelectrochemical study of the electropolymerisation of N-benzylaniline

Authors
  • Malinauskas, Albertas1
  • Holze, Rudolf1
  • 1 Technische Universität Chemnitz, Institut für Chemie, D-09107 Chemnitz, Germany e-mail: [email protected], DE
Type
Published Article
Journal
Journal of Solid State Electrochemistry
Publisher
Springer-Verlag
Publication Date
Sep 01, 1999
Volume
3
Issue
7-8
Pages
429–436
Identifiers
DOI: 10.1007/s100080050178
Source
Springer Nature
Keywords
License
Yellow

Abstract

The electropolymerisation of N-benzylaniline (NBA) at transparent ITO glass electrodes was investigated with in situ UV-visible spectroelectrochemistry. An intermediate was found to be generated during electrolysis as the precursor of poly(N-benzylaniline) (PNBA). The intermediate, which shows an absorbance band at λ = 460 nm, is able to react spontaneously with NBA, forming a polymeric end product, which is deposited on the electrode surface. UV-Vis spectra were obtained with PNBA-modified electrodes at various electrode potentials. It was shown that the colouration of the PNBA film after a positive-going potential step proceeds ca. 5 times slower than its discolouration after the reverse negative-going potential step. Anodic degradation of PNBA film was shown to proceed when holding the electrode at a sufficiently high positive potential. A linear dependence between the first-order degradation rate constant (k/s−1) and electrode potential (E/V) was found in the potential range of ERHE = +0.8 to +1.1 V: log k = a + bE, where a = −8.75 and b = 5.45 are empirical coefficients. In the whole spectral range investigated, the degradation of PNBA was found to proceed faster as compared to that of polyaniline (for polyaniline, coefficients a = −12.7 and b = 8.96 were obtained in the potential range of ERHE = +0.85 to +1.1 V). The electrooxidation of hydroquinone, as well as the electroreduction of benzoquinone, were shown to proceed at PNBA-modified electrodes. In these processes, PNBA was shown to play the role of an electron mediator between the ITO electrode and solution phase redox species.

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