The influence of polyacid nature on poly(3,4-ethylenedioxythiophene) electrosynthesis and its spectroelectrochemical propertiesстатья
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Дата последнего поиска статьи во внешних источниках: 26 декабря 2017 г.
Аннотация:The present study is aimed to elucidate main
structural features of polymeric sulfonic acids (the rigidity
of main chain, the distance between sulfonic groups on
the chain, the hydrophobicity of main chain or side fragments)
on the course of 3,4-ethylenedioxythiophene
(EDOT) electropolymerization and electronic and chemical
structure of the poly(3,4-ethylenedioxythiophene)
(PEDOT) films obtained. The films were prepared by
electrochemical polymerization in cyclic voltammetry,
potentiostatic, and galvanostatic regimes in aqueous solutions
of different polyacids in the absence of supporting
electrolyte. The effect of the chemical structure of
polyacid on the course and rate of PEDOT synthesis was
traced by electrochemical and in situ UV-Vis spectroscopic
methods. It was shown that the highest rate of EDOT
electropolymerization is achieved in the presence of
flexible-chain polyacid having hydrophobic fragments
(groups) in its structure, followed by hydrophobic rigidchain
polyacids. The lowest rate was observed in the presence
of hydrophilic flexible-chain polyacid. The electronic
and chemical structure of the PEDOT films obtained
was studied by in situ UV-Vis-NIR and Raman
spectroelectrochemistry. The films prepared in the
presence of rigid-chain polyacids at high anodic potentials
demonstrate decreased content of bipolaronic fragments in
their structure, while PEDOT complexes with flexiblechain
polyacids are very much like conventional polymer
prepared in non-aqueous medium. The results are
discussed in terms of conformational state (ability to form
coils and thus concentrate the monomer) of different
polyacids in aqueous solution and hydrophobic interactions
between the polyacids and EDOT.