A UV-visible spectroelectrochemical study of the electropolymerisation of N-benzylaniline |
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Authors: | Albertas Malinauskas Rudolf Holze |
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Institution: | Technische Universit?t Chemnitz, Institut für Chemie, D-09107 Chemnitz, Germany e-mail: rudolf.holze@chemie.tu-chemnitz.de, DE
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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 E
RHE = +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 E
RHE = +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.
Received: 8 January 1999 / Accepted: 27 January 1999 |
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Keywords: | Conducting polymers Poly(N-benzylaniline) UV-visible spectroelectrochemistry Electrocatalysis Mediators |
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