Preparation, characterization and electrocatalytic properties of poly(luminol) and polyoxometalate hybrid film modified electrodes

Hybrid films composed of poly(luminol) and nanometer-sized clusters of polyoxometalate, SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻ have been prepared in acidic aqueous solutions. These films are stable and electrochemically active, and produced on glassy carbon, platinum, gold and transparent semiconductor tin oxide electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study in situ growth of the hybrid poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻. Both the poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻ hybrid films showed four redox couples and the electrochemical properties were compared to SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻. When transferred to various acidity aqueous solutions, the four redox couples and the formal potentials of two hybride film were observed to be pH-dependent. The electrocatalytic reduction of ClO₃⁻, BrO₃⁻, IO₃⁻, S₂O₈²⁻ and NO₂⁻ by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film in an acidic aqueous solution showed an electrocatalytic reduction activity of IO₃⁻ > BrO₃⁻ and ClO₃⁻. The electrocatalytic oxidation of dopamine and epinephrine by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film was also investigated.