Raman spectroelectrochemical study of electrodeposited polyaniline doped with polymeric sulfonic acids of different structures

Polyaniline (PANI) films were prepared by electrochemical polymerization of aniline on Pt-electrode in aqueous medium in the presence of polymeric sulfonic acids distinguished by different flexibility of the polymer chain: (1) poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA, flexible chain); (2) poly(4-styrenesulfonic acid) (PSSA, flexible chain), (3) poly-4,4'-(2,2'-disulfoacid)-diphenylene-iso-phthalamide (i-PASA, semi-rigid chain); and (4) poly-4,4'-(2,2'-disulfoacid)-diphelylenetere- phthalamide (t-PASA, rigid chain). Raman spectroelectrochemical studies using 532 nm laser excitation were carried out in aqueous HCl. The conventional HCl-doped PANI films were also studied for comparison. The results allowed one to distinguish the potential-dependent vibrations belonging to PANI and potential-independent vibrations belonging to the polyacids. In addition, amide C=O vibration was separated in the spectra by comparing the results for amide-containing (PAMPSA, i-PASA, and t-PASA) and amide-free (PSSA) PANI-polyacid complexes. The films of PANI-polyacid complexes demonstrated increased content of radical cation moieties at low potentials compared to PANI-HCl films.