Electrochemical degradation and mineralisation of organic dyes in aqueous nitrate solutions

Electrochemical treatment of organic matter for environmental remediation necessitates the development of cheap and robust electrodes that are chemically and structurally stable. To address this challenging requirement, we demonstrate a new electrochemical approach using a simple copper electrode under cathodic conditions to electrochemically generate reactive nitrosonium ions for the degradation of different classes of synthetic organic dyes. This could be achieved in an aqueous HNO₃/KNO₃ electrolyte at a relatively low cathodic potential of -0.5 V RHE at room temperature. UV-visible absorption spectroscopy, Raman spectroscopy, liquid chromatography - mass spectrometry and total organic carbon measurements revealed the rapid decolorisation and mineralisation of several dye types such as triarylmethane dyes (crystal violet, cresol red), an azo dye (methyl orange) as well as a sulfur containing thiazine dye (toluidine blue). The total organic carbon content of a 50 mg L^-1 methyl orange solution was found to decrease by 83% after 1 h of electrolysis. Promisingly, locally sourced river and creek water samples spiked with 50 mg L^-1 methyl orange were also successfully treated for up to 6 cycles at a simple Cu electrode, demonstrating potential for the remediation of polluted waterways.