Poly(3,4-ethylenedioxythiophene) Electrosynthesis in the Presence of Mixtures of Flexible-Chain and Rigid-Chain Polyelectrolytes

The electrochemical synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) was first carried out in the presence of mixtures of flexible-chain and rigid-chain polyacids and their Na-salts. Earlier on with the example of polyaniline, we have shown the non-additive effect of the rigid-chain component of polyacid mixtures on the electrodeposition of polyaniline films, their morphology and spectroelectrochemical properties. In this study, we confirmed the non-additive effect and showed that such mixed PEDOT–polyelectrolyte films possess unique morphology, spectroelectrochemical and ammonia sensing properties. The electrosynthesis was carried out in potential cycling, galvanostatic and potentiostatic regimes and monitored by in situ UV–Vis spectroscopy. UV–Vis spectroelectrochemistry of the obtained PEDOT–polyelectrolyte films revealed the dominating influence of the rigid-chain polyacid on the electronic structure of the mixed complexes. The mixed PEDOT–polyacid films demonstrated the best ammonia sensing performance (in the range of 5 to 25 ppm) as compared to the films of individual PEDOT–polyelectrolyte films.

Physical-Chemical Effects of Nanoparticles on Electropolymerized Polyaniline

The incorporation of nanoparticles on polymer films is possible to obtain materials with desired properties. In the present work, we address the physical-chemical influence of nanoparticles in polymer films by producing and characterizing polyaniline hybrids with SiO2 and Au nanoparticles and comparing them with films with TiO2 nanoparticles. The hybrid films were characterized by SEM, EDS, UV-Vis, AFM, Raman, and cyclic voltammetry. Unlike TiO2 nanoparticles, SiO2 and Au nanoparticles do not promote any noticeable change in polyaniline oxidation state in less acid environments (pH 5.9 and 6.15). However, in those environments, the presence of nanoparticles significantly increases the film's conductivity. At a pH of 1.5 and 3.9, all three kinds of nanoparticles are screened by ions from the solution diminishing their physical-chemical effects on polyaniline. Thus, our results suggest that, in general, nanoparticles don't have any physical-chemical effects on polyaniline films when deposited in acid enough environments but can change their physical and chemical properties when deposited in less acid environments.

Secondary Dopants of Electrically Conducting Polyanilines

Secondary dopants and the doping methods were identified for increasing the electrical conductivity of a highly processable and a primarily doped polyaniline dinonylnaphthalene sulfonic acid (PANI-DNNSA). The secondary doping was carried out using film, solution, and vapor doping methods. The doping methods and functional groups of secondary dopants were observed to play a critical role for inducing electrical characteristics of polyaniline. When secondary film doping method and p-toluenesulfonic acid were used, the electrical conductivity of the secondary doped polyaniline was measured to be increased from 0.16 to 334 S/cm. A novel vapor annealing doping method was developed to incorporate secondary dopants into solution cast polyaniline films.