Removal of recalcitrant organic pollutants by degradation or mineralization from industrial waste streams is continuously being explored to find viable options to apply on the commercial scale. Herein, we propose a titanium nanotube array (based on a non-ferrous Fenton system) for the successful degradation of a model contaminant azo dye, methyl orange, under simulated solar illumination. Titanium nanotube arrays were synthesized by anodizing a titanium film in an electrolyte medium containing water and ethylene glycol. Characterization by SEM, XRD, and profilometry confirmed uniformly distributed tubular arrays with 100 nm width and 400 nm length. The non-ferrous Fenton performance of the titanium nanotube array in a minimal concentration of H2O2 showed remarkable degradation kinetics, with a 99.7% reduction in methyl orange dye concentration after a 60 min reaction time when illuminated with simulated solar light (100 mW cm-2, AM 1.5G). The pseudo-first-order rate constant was 0.407 µmol-1 min-1, adhering to the Langmuir-Hinshelwood model. Reaction product analyses by TOC and LC/MS/MS confirmed that the methyl orange was partially fragmented, while the rest was mineralized. The facile withdrawal and regeneration observed in the film-based titanium nanotube array photocatalyst highlight its potential to treat real industrial wastewater streams with a <5% performance drop over 20 reaction cycles.
Keywords: advanced oxidation process; methyl orange; non-ferrous Fenton reaction; photocatalysis; titanium nanotube.