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.

Carbon nanodots (C-dots) with ultrasmall size possessing large surface-to-volume ratio are expected to improve their performance in sensing and catalytic applications. Here, we present a simple strategy to synthesis ultrasmall C-dots using double-pulse femtosecond laser ablation in solution. The size of C-dots reaches minimum value of ∼1 nm when the delay between the pulses was approaching the electron-ion relaxation time. In this case, the mean sizes of C-dots in double-pulse ablation are even smaller than that obtained in single-pulse ablation with the same laser fluence due to the suppression of rarefaction wave by the shock wave created by the second pulse. Furthermore, abundant functional groups are created on the surface of C-dots in double-pulse ablation because of reheating the nascent ablated materials by the second pulse. These results demonstrate that the double-pulse technique is therefore an effective strategy beyond single-pulse ablation to synthesis ultrasmall C-dots with abundant surface functional groups as well as other nanoparticle for catalytic and sensing applications.

Fluorine-doped tin oxide (FTO) thin films were deposited on glass substrates using ultrasonic spray pyrolysis (USP) at a fixed substrate temperature of 400 °C and various Fluorine/Tin (F/Sn) atomic ratios of 0, 0.1, 0.5, and 1.0. Effects of F/Sn atomic ratios on structural-morphological, compositional, electrical, optical, and nanomechanical properties of the FTO thin films were systematically studied. The FTO films exhibited a tetragonal structure with preferred orientations of (110), (200), and (211), and polycrystalline morphology with spear-like or coconut shell-like particles on the surfaces. The presence of F-doping was confirmed by XPS results with clear F1s peaks, and F-concentration was determined to be 0.7% for F/Sn = 0.1 and 5.1% for F/Sn = 0.5. Moreover, the resistivity of FTO films reduced remarkably from 4.1 mΩcm at F/Sn = 0 to 0.7 mΩcm at F/Sn = 1, primarily due to the corresponding increase of carrier concentration from 2 × 10²⁰ cm⁻³ to 1.2 × 10²¹ cm⁻³. The average optical transmittance of the films prepared at F/Sn of 0–0.5 was over 90%, and it decreased to 84.4% for the film prepared at F/Sn = 1. The hardness (H) and Young’s modulus (E) of the FTO films increased when the F/Sn ratios increased from 0 to 0.5, reaching maximum values of H = 12.3 ± 0.4 GPa, E = 131.7 ± 8.0 GPa at F/Sn = 0.5. Meanwhile, the H and E reduced considerably when the F/Sn ratio further increased to 1.0, following the inverse Hall-Petch effect approximately, suggesting that the grain boundary effect played a primary role in manipulating the nanomechanical properties of the FTO films. Furthermore, favorable mechanical properties with large H/E_f and $H^3/E_f^2$ ratios were found for the FTO film prepared at F/Sn = 0.5, which possessed high crystallinity, large grain size, and compact morphology.

Nitrogen-doped TiO₂ nanotube arrays (N-TNAs) were successfully fabricated by a simple thermal annealing process in ambient N₂ gas at 450 °C for 3 h. TNAs with modified morphologies were prepared by a two-step anodization using an aqueous NH₄F/ethylene glycol solution. The N-doping concentration (0–9.47 at %) can be varied by controlling N₂ gas flow rates between 0 and 500 cc/min during the annealing process. Photocatalytic performance of as-prepared TNAs and N-TNAs was studied by monitoring the methylene blue degradation under visible light (λ ≥ 400 nm) illumination at 120 mW·cm⁻². N-TNAs exhibited appreciably enhanced photocatalytic activity as compared to TNAs. The reaction rate constant for N-TNAs (9.47 at % N) reached 0.26 h⁻¹, which was a 125% improvement over that of TNAs (0.115 h⁻¹). The significant enhanced photocatalytic activity of N-TNAs over TNAs is attributed to the synergistic effects of (1) a reduced band gap associated with the introduction of N-doping states to serve as carrier reservoir, and (2) a reduced electron‒hole recombination rate.