X-ray absorption spectroscopy of iron-doped conducting polymers

X-ray absorption spectroscopy (XAS) measurements were performed at the Fe K edge to determine the iron local structure in chemically prepared polyaniline (PANI) and polypyrrole (PPy) samples prepared with FeCl3 as an oxidant. The samples were conditioned at different pHs by an acid–base treatment. In both as synthesized-doped polymers, the observed dispersed Fe atoms were predominantly coordinated to chlorine as Fe(III)Clx species, where x=6 for PANI and x=4 for PPy samples suggesting that the polymer–counteranion bonding is weaker than the iron–chelate one. For the PANI samples submitted to basic treatment, three different sets of Fe distances were found: five Fe–O at 2.00 Å, three Fe–Fe at approximately 2.80 Å and five Fe–Fe at 3.00 Å and the near-edge spectra showed the presence of octahedrally coordinated Fe+3. These results strongly suggest the presence of small oxide/hydroxide aggregates. Similar data were obtained for PPy treated with NH4OH.