An Unusual Electrochemical Reductive Cleavage of Azo Dye into Highly Redox Active Copolymeric Aniline Derivatives on a MWCNT Modified Electrode Surface at Neutral pH and Its Electroanalytical Features

Abstract

Developments of new decomposition or degradation methods of environmentally hazardous azo dyes from textile industries are very important. Usually, strong acid-based chemical/electrochemical and neutral pH-based bacterial decomposition methods were widely used. Here, we report a mild, simple, and facile electrochemical method for decomposition of azo dye (Sudan yellow; SY) into a highly redox active copolymer of polyanilines via aniline derivatives as intermediates on a MWCNT modified glassy carbon electrode (GCE/MWCNT) surface unusually in a neutral pH using phosphate buffer solution (PBS) (GCE/MWCNT@SY-CoPANI_pH7). One of the intermediate products, aniline (<i>M</i>_w = 93 mol g^–1, calculated) was identified by an in situ cyclic voltammetry-electrochemical quartz crystal balance experiment. No such SY electrochemical reaction was observed on a naked GCE surface. Physico-chemical characterizations by TEM, Raman, IR, and UV–vis spectroscopic methods supported the formation of polymeric product on MWCNT surface (GCE/MWCNT@SY-CoPANI_pH7). Electroanalytical performance of this new electrode was tested using ascorbic acid (AA) and Fe­(CN)₆^3–, as models. Interestingly, a dilute solution of Nafion (Nf) casted modified electrode system (GCE/MWCNT@SY-CoPANI_pH7/Nf) showed improved electroanalytical performance, unlike the conventional Nafion modified system (GCE/MWCNT/Nf) with vanished peak current response due to the electrostatic repulsive interaction between the anionic AA (p<i>K</i>_a = 4.10), Fe­(CN)₆^3– ion, and anionic sulfonic acid groups in Nafion. A zwitter ionic complex between a polaronic copolyaniline and sulfonic acid of Nafion is proposed as a possible structure for the newly developed hybrid system. Using the GCE/MWCNT@SY-CoPANI_pH7/Nf, a selective flow injection analysis of AA has been demonstrated as an analytical application with good recovery values