Bismuth-Doped Tin Oxide-Coated Carbon Nanotube Network: Improved Anode Stability and Efficiency for Flow-Through Organic Electrooxidation

摘要

In this study, a binder-free, porous, and conductive 3D carbon-nanotube (CNT) network uniformly coated with bismuth-doped tin oxide (BTO) nanoparticles was prepared via a simple electrosorption—hydrothermal method and utilized for the electrooxidative nitration of organics. The BTO-CNT nanocomposite was characterized by scanning electron microscopy, thermogravimetric analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, linear sweep voltammetry, and Tafel analysis. The submonolayer BTO coating is composed of 3.9 ± 1.5 nm diameter nanoparticles (NPs). The oxygen-evolution potential of the BTO-CNT nanocomposite was determined to be 1.71 V (vs Ag/AgCl), which is 440 mV higher than an uncoated CNT anode. Anodic stability, characterized by CNT oxidative corrosion to form dissolved species, indicated that the BTO-CNT incurred negligible corrosion up to V_(anode), = 2.2 V, whereas the uncoated CNT was compromised at V_(anode) ≥ 1.4 V. The effect of metal oxide-nanoparticle coating on anodic performance was initially studied by oxalate oxidation followed by total organic carbon (TOC) and chemical oxygen demand (COD) analysis. The BTO-CNT displayed the best performance, with ～98% oxalate oxidation (1.2 s filter residence time) and current efficiencies in the range of 32 to >99%. The BTO-CNT anode energy consumption was 25.7 kW h kgCOD~(-1) at ～93% TOC removal and 8.6 kW h kgCOD~(-1) at ～50% TOC removal, comparable to state-of-the-art oxalate oxidation processes (22.5-81.7 kW h kgCOD~(-1)). The improved reactivity, current efficiency, and energy consumption are attributed to the increased conductivity, oxygen-evolution potential, and stability of the BTO-CNT anode. The effectiveness and efficiency of the BTO-CNT anode as compared to the uncoated CNT was further investigated by the electrooxidative filtration of ethanol, methanol, formaldehyde, and formate, and it was determined to have TOC removals 2 to 8 times greater, mineralization current efficiencies 1.5 to 3.5 times greater, and energy consumption 4 to 5 times less than the uncoated CNT anode. Electrooxidation and anode passivation mechanisms are discussed.