The Electrochemical Oxidation and Polymerization of Polycyclic Hydrocarbons

Abstract

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Electrically conducting polymers: a review of the electropolymerization reaction, of the effects of chemical structure on polymer film properties, and of applications towards technology

“…However, the n values derived from voltammograms really represent the total reaction at the electrode surface and can include secondary chemical reactions that accompany the electropolymerization reaction, such as dimerization reactions to form soluble products. This has been observed in the electropolymerization reaction of pyrene (6), and will be discussed below (Sect. IIIf) in more detail.…”

“…11, the electrochemically estimated n value for pyrene (n = 1.7) is lower than would ordinarily be expected for these film-forming reactions, i.e., less than 2.0. This may result from the presence of competitive reaction pathways which have different electrochemical stoichiometries and different products, e.g., polymer versus soluble products (6). Thus, the n value of 1.7 is an apparent n value (nap,) for the total reaction.…”

“…Since nap, and n, are both known (Table l), the fraction of pyrene monomer which leads to polymer can be estimated. This assumes that the competing reaction is a dimerization reaction with n = 1, and that it is the only competing reaction (6). Thus, if f is the fraction of monomer which electropolymerizes, then (1 -f ) is the fraction that forms soluble species.…”

“…From eq. [6], where n, is 2.3 1 and is the n value of polypyrene determined from elemental analysis, and n, is 1.0 and is the n value for dimerization. Thus, the fraction of pyrene monomers that gives rise to polymers is 0.54; i.e., approximately half of the monomers are used in the film-forming reaction.…”

Pyrene functionalized single-walled carbon nanotubes as precursors for high performance biosensors

“…The electropolymerization was further investigated by repeated potential cycling over the range 0 and 1.5 V. The oxidation peak decreased drastically for the second and almost disappears for the following scans indicating the formation of an insulating poly(pyrene-biotin) layer. This unusual behaviour for electrogenerated polypyrene films [13] can be related to the incorporation of the biotin groups in the film during polymer growth as observed for the pyrrole equivalent by Cosnier et al [14,15]. Nevertheless, upon transfer into a CH 3 CN + 0.1 M TBAP monomer free solution, the cyclic voltammogram of the resulting electrode between 0 and 1 V shows a reversible peak system at E 1/2 = 0.4 V with an anodic-cathodic peak separation: (Fig.…”