Radiation‐Induced Synthesis of Nanostructured Conjugated Polymers in Aqueous Solution: Fundamental Effect of Oxidizing Species

Abstract

Synthesis of conjugated poly(3,4-ethylenedioxythiophene) (PEDOT) polymers is achieved through the radiolysis of N2O-saturated aqueous solutions of 3,4-ethylenedioxythiophene by using two different oxidizing species: HO(·) (hydroxyl) and N3(·) (azide) radicals. Both oxidative species lead to self-assembled polymers that are evidenced in solution by cryotransmission electron microscopy and UV/Vis absorption spectroscopy and, after centrifugation and deposition, by scanning electron microscopy and attenuated total reflectance FTIR techniques. Whereas HO(·) radicals lead to PEDOT-OH globular nanostructures with hydrophilic properties, N3(·) radicals enable the formation of amphiphilic PEDOT-N3 fibrillar nanostructures. These results, which highlight the differences in the intermolecular interaction behaviors of the two kinds of PEDOT polymers, are discussed in terms of polymerization mechanisms.

An alternative radiolytic route for synthesizing conducting polymers in an organic solvent

“…As observed, the prepared EDOT solution exhibits two absorption maxima at 242 and 259 nm which are features of the p-p* electronic transitions in the thiophene rings within the dichloromethane solvent. 16 This is consistent with the fact that pure thiophene molecules absorb light in the UV region between 225 and 245 nm, this absorption being ascribed to the p-p* transition. 30 Within this context, EDOT showed good solubility in dichloromethane which is higher than 20 mM in concentration (results not shown).…”

“…The absence of these bands after irradiation implies the formation of PEDOT polymers thanks to a,a 0 -coupling reactions. 16 The infrared spectra obtained after irradiation reveal the typical bands of the PEDOT polymers. Nevertheless, one can note the presence, whatever the irradiation dose, of a less common infrared band located at 1640 cm À1 .…”

“…14 Apart from the traditional methods of polymers synthesis, ionizing radiation induced polymerization by g-rays or accelerated electrons is not commonly used in the field of CP synthesis. 15 In previous studies, our group has developed a new methodology based on radiation chemistry to polymerize some of those conducting polymers in aqueous solutions [16][17][18][19] thanks to the oxidation of dissolved organic monomers by oxidizing radicals in situ produced in the medium during water radiolysis. Additionally, pulse radiolysis was used to study and to understand the growth mechanism of PEDOT polymers initiated by these radicals in aqueous solution.…”

Flexible Electrodes for Supercapacitors Based on the Supramolecular Assembly of Biohydrogel and Conducting Polymer

“…As observed, apparently such microstructure results from the assembly of lamellar architectures, suggesting that PHMeDOT organizes according to a foldedchain model. 50 Moreover, SEM cross section images (Figure 4d) demonstrate that the conductive…”

Recent progress on nanostructured conducting polymers and composites: synthesis, application and future aspects

“…Lee et al [85] reported the synthesis of highly uniform PPy particles (100~500 nm in diameter) with a good electrical property by in-situ γ-irradiation/induced chemical oxidative polymerization method. Remita et al [86,87] did a systematical investigation on radiolytic synthesis of PEDOT nanostructures and related mechanism.…”