Self-assembled polyaniline 12-tungstophosphate micro/nanostructures

Polyaniline (PANI) micro/nanostructures were synthesized by the external-template-free oxidative polymerization of aniline in aqueous solution of 12-tungstophosphoric acid (WPA), using ammonium peroxydisulfate (APS) as an oxidant and starting the oxidation of aniline from slightly acidic media (pH 5.4–5.9). The effect of the initial weight ratio of WPA to aniline on molecular structure, morphology, and physicochemical properties of polyaniline 12-tungstophosphate (PANI-WPA) was investigated by FTIR, Raman and inductively coupled plasma optical emission (ICP-OES) spectroscopies, elemental analysis, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and conductivity measurements. The morphological change of polymerization products during a single polymerization process, from non-conducting submicro-/microspherical oligoaniline intermediates to semiconducting PANI-WPA consisted of self-assembled nanotubes and/or nanorods co-existing with submicro-/microspheres, has been revealed by SEM and TEM. The average diameter of nanorods in PANI-WPA samples decreased with increasing the initial WPA/aniline weight ratio. The incorporation of 12-tungstophosphate counter-ions into PANI matrix has been proved by FTIR, Raman and ICP-OES spectroscopies, TGA and DTA analysis. Electrical conductivity of PANI-WPA increased in the range (2.5–5.3) × 10−3 S cm−1 with the increase of the initial WPA/aniline weight ratio. The presence of branched structures and phenazine units besides the ordinary paramagnetic and diamagnetic emeraldine salt structural features in PANI-WPA was proved by FTIR and Raman spectroscopies.