Mineralization of Methyl Orange azo dye by processes based on H2O2 electrogeneration at a 3D-like air-diffusion cathode

Abstract

This work addresses the mineralization of the widely used Methyl Orange (MO) azo dye by technologies based on H₂O₂ electrogeneration at a 3D-like air-diffusion cathode. These include two Fe²⁺-catalyzed processes such as electro-Fenton (EF) and photoelectro-Fenton (PEF). Bulk electrolyses were performed in a recirculation flow plant, in which the Eco-Cell filter-press electrochemical reactor was connected in series with a UVA photoreactor. The former reactor was equipped with a Ti|Ir-Sn-Sb oxide plate anode alongside a 3D-like air-diffusion cathode made from graphite felt and hydrophobized carbon cloth, aimed at electrogenerating H₂O₂ on site. The influence of current density (j), volumetric flow rate (Q) and initial MO concentration was examined. The greatest oxidation power corresponded to PEF process. The best operation conditions to treat 30 mg L^-1 of total organic carbon of MO in a 50 mM Na₂SO₄ solution by PEF were found at 0.50 mM Fe²⁺, pH 3.0, j = 20 mA cm^-2 and Q = 2.0 L min^-1, obtaining 100% and 94% of color and TOC removals at 30 and 240-300 min, respectively. This accounted for 35% of mineralization current efficiency and 0.12 kWh (g TOC)^-1 of energy consumption at the end of the electrolysis. The oxidation power of EF and PEF was compared with that of anodic oxidation (AO), and the sequence obtained was: PEF > EF > AO. The dye was gradually degraded, yielding non-toxic short carboxylic acids, like maleic, fumaric, formic, oxalic and oxamic, whose Fe(III) complexes were rapidly photolyzed.

Keywords: Azo dye; Gas-diffusion electrode; Hydrogen peroxide; Photoelectro-fenton; Water treatment.