PFeW11-doped polymer film modified electrodes and their electrocatalytic activity for H2O2 reduction Original Research Article

A study of electrochemical and electrocatalytic properties, toward H2O2 reduction, of the [PFeW11O39]−4 polyoxoanion in solution as well as immobilized in partially oxidized polypyrrole (pPy) and in polyvinyl alcohol bearing styrylpyridinium groups (PVA) films is reported. Using cyclic voltammetry at different pH values and scanning rates it was observed that: (i) the two bielectronic waves corresponding to the tungstate-oxo cage are pH-dependent; (ii) the Fe center of the polyoxoanion has an excellent electrocatalytic effect on H2O2 reduction, giving a catalytic efficiency and an electrode sensitivity, both higher when dissolved than when immobilized onto electrode surface; and (iii) the one-step method used to obtain the pPy-doped film assures a greater amount of immobilized polyoxoanion than the ionic-exchange method used for PVA films. From rotating-disk electrode (RDE) measurements, the polyoxoanion diffusion coefficient was estimated at 4.1×10−6 cm2 s−1, which agrees to that obtained by cyclic voltammetry, 3.9×10−6 cm2 s−1, and the heterogeneous rate constant was found to vary between 3.5×10−3 and 1.9×10−3 cm s−1 at a variation of the electrode potential from 30 to −30 mV vs. SCE. The best amperometric response observed for the PFeW11-doped pPy membrane, showed a linear response to H2O2 additions up to 9 mM and a sensitivity of 4.8 mA M−1 H2O2 in the first day of utilization.