Blue TiO nanotube electrocatalytic membrane electrode for efficient electrochemical degradation of organic pollutants.

In this study, a Ti-doped TiO porous membrane (Blue TiO/Ti) was fabricated and employed for electrochemical degradation of organic pollutants in the single-pass flow-through mode. Characterizations including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microcopy (SEM) and energy dispersive spectroscopy (EDS) verified that Ti-doped anatase TiO with nanotube structures was successfully prepared. Electrochemical analysis including linear sweep voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and electrochemical active surface area (ESA) revealed higher oxygen evolution potential (OEP, 2.23 V vs. Ag/AgCl), larger redox peak current, lower impedance and larger ESA (69 cm/cm) of Blue TiO/Ti compared to the Ti and TiO/Ti membranes. The effects of current density, flow rate and solution environment on the removal of methylene blue (MB) were investigated. The removal rates of various organic pollutants including sulfamethoxazole (SMX), methyl orange (MO), bisphenol A (BPA) and MB could reach 92.2%-99.5%. The quenching experiment proved that hydroxyl radicals (•OH) played the major role in the Blue TiO/Ti based electrochemical system. Furthermore, the degradation pathways of two typical pollutants (SMX and MB) were proposed by analyzing the oxidation products with liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), with the assistance of orbital-weighted Fukui index (f and f) obtained through Density Functional Theory (DFT) calculations. Moreover, toxicity indexes of the oxidation products were obtained and compared to the parent SMX and MB using Toxicity Estimation Software Tool (TEST) software. Finally, the long-term operation performance of the Blue TiO/Ti membrane was evaluated.