Direct electrochemistry and electrocatalysis of anthraquinone-monosulfonate/polyaniline hybrid film synthesized by a novel electrochemical doping-dedoping-redoping method on pre-activated spectroscopically pure graphite surface

Polyaniline (PANI) film in the form of emeraldine salt (ES) doped with anthraquinone-2-sulfonate (AQS) was synthesized by a novel electrochemical doping-dedoping-redoping method on pre-activated spectroscopically pure graphite electrode surface. SEM showed the highly porous microstructure with sponge-like morphology of the AQS/PANI hybrid film, which has more available active sites for facilitating electron transfer and energy efficiency of redox reactions. FTIR and UV-vis spectra demonstrated the incorporation of AQS into the conductive PANI matrix. Cyclic voltammetric (CV), electrochemical impedance spectroscope (EIS), rotating ring-disk electrode (RRDE) and chronoamperometry (CA) techniques indicated that the AQS/PANI composite has high electrocatalytic activity and remarkable stability for the two-electron reduction of oxygen via an electrochemical-chemical mechanism at the base of the porous PANI film. The acid centers of PANI (protonated imine group) played an important role not only in two internal redox transform processes, but also in an external charge transfer reaction during the electrocatalytic reduction of oxygen. The incorporation of anionic AQS groups into PANI matrix to prepare electroactive PANI using the electrochemical doping-dedoping-redoping method is conceptually new, and may be extended to the development of new functional materials from many other conducting polymers and quinonoid compounds for wide applications in catalysis, sensors, molecular electronics, and so on.