Antibiotic residues in aquaculture wastewater are considered as an emerging environmental problem, as they are not efficiently removed in wastewater treatment plants. To address this issue, we fabricated TiO2 nanotube arrays (TNAs), TiO2 nanowires on nanotube arrays (TNWs/TNAs), Au nanoparticle (NP)-decorated-TNAs, and TNWs/TNAs, which were applied for assessing the photocatalytic degradation of eight antibiotics, simultaneously. The TNAs and TNWs/TNAs were synthesized by anodization using an aqueous NH4F/ethylene glycol solution. Au NPs were synthesized by chemical reduction method, and used to decorate on TNAs and TNWs/TNAs. All the TiO2 nanostructures exhibited anatase phase and well-defined morphology. The photocatalytic performance of TNAs, TNWs/TNAs, Au-TNAs and Au-TNWs/TNAs was studied by monitoring the degradation of amoxicillin, ampicillin, doxycycline, oxytetracycline, lincomycin, vancomycin, sulfamethazine, and sulfamethoxazole under ultraviolet (UV)-visible (VIS), or VIS illumination by LC-MS/MS method. All the four kinds of nanomaterials degraded the antibiotics effectively and rapidly, in which most antibiotics were removed completely after 20 min treatment. The Au-TNWs/TNAs exhibited the highest photocatalytic activity in degradation of the eight antibiotics. For example, reaction rate constants of Au-TNWs/TNAs for degradation of lincomycin reached 0.26 min−1 and 0.096 min−1 under UV-VIS and VIS irradiation, respectively; and they were even higher for the other antibiotics. The excellent photocatalytic activity of Au-TNWs/TNAs was attributed to the synergistic effects of: (1) The larger surface area of TNWs/TNAs as compared to TNAs, and (2) surface plasmonic effect in Au NPs to enhance the visible light harvesting.
This study presents a multi-residue method for simultaneous qualitative and quantitative analysis of eight antibiotics from some common classes, including beta-lactam, tetracyclines, lincosamides, glycopeptides, and sulfonamides in 39 aquaculture and river water samples from the Mekong Delta (Vietnam) using liquid chromatography-tandem mass spectrometry (LC-MS/MS). As a result, doxycycline (DXC), oxytetracycline (OTC), lincomycin (LCM), sulfamethoxazole (SMX), and sulfamethazine (SMZ) were detected with high frequency over 65% and an average concentration of 22.6–76.8 ng·mL−1. The result suggests that antibiotic residues in the aquaculture and river waters are considered as an emerging environmental problem of the region. To address this issue, we fabricated the well-defined TiO2 nanotube arrays (TNAs) and nanowires on nanotube arrays (TNWs/TNAs) using the anodization method. The TNAs had an inner tube diameter of ~95 nm and a wall thickness of ~25 nm. Meanwhile, the TNWs/TNAs had a layer of TiO2 nanowires with a length of ~6 µm partially covering the TNAs. In addition, both TNAs and TNWs/TNAs had pure anatase phase TiO2 with (101) and (112) dominant preferred orientations. Moreover, the TNAs and TNWs/TNAs effectively and rapidly degraded the antibiotic residues under UV-VIS irradiation at 120 mW/cm2 and obtained over 95% removal at 20 min. Indeed, the photocatalytic reaction rate constants (k) were in the range of 0.14–0.36 min−1 for TNAs, and 0.15–0.38 min−1 for TNWs/TNAs. Noticeably, the k values of TNWs/TNAs were slightly higher than those of TNAs for LCM, DXC, OTC, SMZ, and SMX that could be attributed to the larger surface area of TNWs/TNAs than TNAs when TNWs/TNAs had an additional ~6μm TNWs top layer.
In this study, TiO2 nanowires on TiO2 nanotubes arrays (TNWs/TNAs) and Au-decorated TNWs/TNAs nanostructures are designed and fabricated as a new type of photoanode for photoelectrochemical (PEC) water splitting. The TNWs/TNAs were fabricated on Ti folds by anodization using an aqueous NH4F/ethylene glycol solution, while Au nanoparticles (NPs) and Au nanorods (NRs) were synthesized by Turkevich methods. We studied the crystal structure, morphology, and PEC activity of four types of nanomaterial photoanodes, including TNWs/TNAs, Au NPs- TNWs/TNAs, Au NRs-TNWs/TNAs, and Au NPs-NRs-TNWs/TNAs. The TiO2 and Au-TiO2 samples exhibited pure anatase phase of TiO2 with (0 0 4), (1 0 1), and (1 0 5) preferred orientations, while Au-TiO2 presented a tiny XRD peak of Au (111) due to a small Au decorated content of 0.7 ± 0.2 at.%. In addition, the samples obtained a well-defined and uniformed structure of TNAs/TNWs; Au NPs (size of 19.0 ± 1.9 nm) and Au NRs (width of 14.8 ± 1.3 nm and length of 99.8 ± 15.1 nm) were primarily deposited on TNWs top layer; sharp Au/TiO2 interfaces were observed from HRTEM images. The photocurrent density (J) of the photoanode nanomaterials was in the range of 0.24–0.4 mA/cm2. Specifically, Au NPs-NRs- decorated TNWs/TNAs attained the highest J value of 0.4 mA/cm2 because the decoration of Au NPs and Au NRs mixture onto TNWs/TNAs improved the light harvesting capability and the light absorption in the visible-infrared region, enhanced photogenerated carriers’ density, and increased electrons’ injection efficiency via the localized surface plasmon resonance (LSPR) effect occurring at the Au nanostructures. Furthermore, amongst the investigated nanophotocatalysts, the Au NPs-NRs TNWs/TNAs exhibited the highest photocatalytic activity in the degradation of methylene blue with a high reaction rate constant of 0.7 ± 0.07 h−1, which was 2.5 times higher than that of the pristine TNWs/TNAs.
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