Photocatalytic processes as a potential solution for plastic waste management

Plastics have become a critical environmental problem due to their widespread use, high physico-chemical stability and the inefficiency of wastewater treatments. Despite the efforts to reduce production and to increase reuse and recycling, the current strategies for plastic waste treatment are not suitable to handle with the growing demand of plastics and the concomitant waste in an environmentally friendly manner. Herein, we review the existing strategies for the treatment of plastic waste, highlighting photocatalytic processes as a potential solution for the degradation of plastics. The possibility of incorporating photocatalysts to plastics during the production process could enhance their light-activated biodegradability. Parallelly, photocatalysts can be employed during waste treatment processes of non-biodegradable stable plastics. The scarcely studied factors affecting plastic photocatalytic degradation, namely catalyst type, reactor configuration, and radiation source (intensity and wavelength), are discussed, highlighting the role that photocatalytic processes can play in the future of plastic management. Finally, relevant quantification methods for measuring the photo-degradation of plastics are overviewed. We believe that photocatalysis can be an environmentally friendly strategy both to increase the biodegradability of plastics and to treat plastic waste. With this novel comprehensive overview, we hope to stimulate further research and innovation in this field.Xunta de Galicia | Ref. ED481B 2019/091Universidade de Vigo/CISU

Track geometry monitoring by an on-board computer-vision-based sensor system

This article illustrates some outcomes of the EU project Assets4Rail, founded within the Shift2Rail Joint Undertaking. Nowadays, Track recording vehicles (TRV) are equipped with laser/optical systems with inertial units to monitor track geometry (TG). Dedicated trains and sophisticated measurement equipment are difficult, costly to acquire and maintain. So the time interval between two TRV recordings of the TG on the same line section cannot be too close (twice per month to twice per year). Recently, infrastructure managers have been more interested in using commercial trains to monitor track condition in a cost-effective manner. TRVs' expensive and constantly maintained optical systems make them unsuitable for commercial fleets. On-board sensor systems based on indirect measurements such as accelerations have been developed in various studies. While detecting the vertical irregularity is a straightforward method by doubling the recorded acceleration, it is yet an unsolved issue for lateral irregularities due to the complicated relative wheel-rail motion. The proposed system combines wheel-rail transversal relative position data with on-board lateral acceleration sensors to detect lateral alignment issues. It includes a functional prototype of an on-board computer vision sensor capable of monitoring Lateral displacement for TG measurements. This eliminates measurement errors due to wheelset transverse displacements relative to the track, which is essential for calculating lateral alignment. The sensor system prototype was tested in Italy at 100 km/h on the Aldebaran 2.0 TRV of RFI, the main Italian Infrastructure Manager. It was found that the estimated lateral displacement well corresponds to the lateral alignment acquired by the Aldebaran 2.0 commercial TG inspection equipment. Moreover, due to the lack of measurement of the acceleration on board the Aldebaran 2.0 TRV, a Simpack® simulation provide with axle box acceleration values, to evaluate the correlation between them, LDWR and track alignment issues

Design and performance of novel self-cleaning g-C3N4/PMMA/PUR membranes

In the majority of photocatalytic applications, the photocatalyst is dispersed as a suspension of nanoparticles. The suspension provides a higher surface for the photocatalytic reaction in respect to immobilized photocatalysts. However, this implies that recovery of the particles by filtration or centrifugation is needed to collect and regenerate the photocatalyst. This complicates the regeneration process and, at the same time, leads to material loss and potential toxicity. In this work, a new nanofibrous membrane, g-C3N4/PMMA/PUR, was prepared by the fixation of exfoliated g-C3N4 to polyurethane nanofibers using thin layers of poly(methyl methacrylate) (PMMA). The optimal amount of PMMA was determined by measuring the adsorption and photocatalytic properties of g-C3N4/PMMA/PUR membranes (with a different PMMA content) in an aqueous solution of methylene blue. It was found that the prepared membranes were able to effectively adsorb and decompose methylene blue. On top of that, the membranes evinced a self-cleaning behavior, showing no coloration on their surfaces after contact with methylene blue, unlike in the case of unmodified fabric. After further treatment with H2O2, no decrease in photocatalytic activity was observed, indicating that the prepared membrane can also be easily regenerated. This study promises possibilities for the production of photocatalytic membranes and fabrics for both chemical and biological contaminant control.Web of Science124art. no. 85

Conception, synthèse et fonctionnalisation de nanoparticules de très petite taille pour des applications en bio-imagerie

This thesis focuses on the synthesis, characterization, functionalization and in vitro and in vivo investigation of different kinds of ultrasmall nanoparticles (silicon nanoparticles: Si NPs; carbon dots: CQDs; silica-coated cobalt NPs: Co@SiO2 NPs) which exhibit luminescence or magnetic properties and can be functionalized through covalent bonds. All the systems studied are very attractive for in vivo multimodal imaging, which requires the stable anchoring of multiple functionalities on a single nano-sized platform. In this perspective, nanoparticles were functionalized with amine-moieties and, subsequently, coupled with dyes or radiolabels in order to perform in vivo optical or positron emission tomography imaging. When tested in vitro, ultrasmall nanoparticles showed very low cytotoxicity. In vivo experiments gave very promising results since nanoparticles were excreted from the body in short times, mainly through a renal clearance mechanism, with low accumulation in organs.Cette thèse est centrée sur la synthèse, la caractérisation, la fonctionnalisation et les études in vitro et in vivo de différents types de nanoparticules (NPs) de très petite taille (NPs de silicium ; « carbon dots » ; NPs de cobalt couvertes de silice) qui présentent une luminescence ou des propriétés magnétiques et qui peuvent être fonctionnalisées par des liaisons covalentes. Tous les systèmes étudiés sont très intéressants pour l'imagerie multimodale in vivo, ce qui nécessite l'ancrage stable de fonctionnalités multiples sur une seule plate-forme nanométrique. Dans cette perspective, les NPs ont été fonctionnalisées avec des groupements amine et, puis, couplées avec des colorants ou des marqueurs radioactifs afin d'effectuer, in vivo, de l’imagerie optique ou de tomographie d'émission des positrons. Lorsqu’elles sont étudiées in vitro, les NPs ont présenté une cytotoxicité très faible. Les expériences in vivo ont donné des résultats très prometteurs puisque les NPs ont été excrétées par le corps en très peu de temps, principalement par un mécanisme de clairance rénale, avec une faible accumulation dans les organes

Reusable and Antibacterial Polymer-Based Nanocomposites for the Adsorption of Dyes and the Visible-Light-Driven Photocatalytic Degradation of Antibiotics

Adsorption and advanced oxidation processes, especially photocatalysis, are amongst the most common water treatment methodologies. Unfortunately, using each of these techniques independently does not fully eliminate the pollutants of diverse nature, which are present in wastewater. Here, an avenue for multifunctional materials for water treatment is opened by reporting for the first time the preparation, characterization, and study of the properties of a novel multifunctional nanocomposite with both adsorption and visible-light-driven photocatalysis abilities. These multifunctional nanocomposites, namely iron (II, III) oxide/poly(N-isopropylacrylamide-co-methacrylic acid)/silver-titanium dioxide (Fe3O4/P(NIPAM-co-MAA)/Ag-TiO2), are prepared by combining magnetic polymeric microspheres (Fe3O4/P(NIPAM-co-MAA)) with silver-decorated titanium dioxide nanoparticles (Ag-TiO2 NPs). Cationic dyes, such as basic fuchsin (BF), can be adsorbed by the nanocomposites thanks to the carboxylic groups of Fe3O4/P(NIPAM-co-MAA) microspheres. Concomitantly, the presence of Ag-TiO2 NPs endows the system with the visible-light-driven photocatalytic degradation ability toward antibiotics such as ciprofloxacin (CIP) and norfloxacin (NFX). Furthermore, the proposed nanocomposites show antibacterial activity toward Escherichia coli (E. coli), thanks to the presence of silver nanoparticles (Ag NPs). Due to the superparamagnetic properties of iron (II, III) oxide nanoparticles (Fe3O4 NPs), the nanocomposites can be also recycled and reused, after the cleaning process, by using an external magnetic field

Enhanced visible-light photodegradation of fluoroquinolone-based antibiotics and E. coli growth inhibition using Ag-TiO2 nanoparticles

Antibiotics in wastewater represent a growing and worrying menace for environmental and human health fostering the spread of antimicrobial resistance. Titanium dioxide (TiO2) is a well-studied and well-performing photocatalyst for wastewater treatment. However, it presents drawbacks linked with the high energy needed for its activation and the fast electron-hole pair recombination. In this work, TiO2 nanoparticles were decorated with Ag nanoparticles by a facile photochemical reduction method to obtain an increased photocatalytic response under visible light. Although similar materials have been reported, we advanced this field by performing a study of the photocatalytic mechanism for Ag-TiO2 nanoparticles (Ag-TiO2 NPs) under visible light taking in consideration also the rutile phase of the TiO2 nanoparticles. Moreover, we examined the Ag-TiO2 NPs photocatalytic performance against two antibiotics from the same family. The obtained Ag-TiO2 NPs were fully characterised. The results showed that Ag NPs (average size: 23.9 +/- 18.3 nm) were homogeneously dispersed on the TiO2 surface and the photo-response of the Ag-TiO2 NPs was greatly enhanced in the visible light region when compared to TiO2 P25. Hence, the obtained Ag-TiO2 NPs showed excellent photocatalytic degradation efficiency towards the two fluoroquinolone-based antibiotics ciprofloxacin (92%) and norfloxacin (94%) after 240 min of visible light irradiation, demonstrating a possible application of these particles in wastewater treatment. In addition, it was also proved that, after five Ag-TiO2 NPs re-utilisations in consecutive ciprofloxacin photodegradation reactions, only a photocatalytic efficiency drop of 8% was observed. Scavengers experiments demonstrated that the photocatalytic mechanism of ciprofloxacin degradation in the presence of Ag-TiO2 NPs is mainly driven by holes and OH radicals, and that the rutile phase in the system plays a crucial role. Finally, Ag-TiO2 NPs showed also antibacterial activity towards Escherichia coli (E. coli) opening the avenue for a possible use of this material in hospital wastewater treatment.Web of Science1123139911398

A Supramolecular Nanoassembly of Lenvatinib and a Green Light-Activatable NO Releaser for Combined Chemo-Phototherapy

The chemotherapeutic Lenvatinib (LVB) and a nitric oxide (NO) photodonor based on a rhodamine antenna (RD-NO) activatable by the highly compatible green light are supramolecularly assembled by a β-cyclodextrin branched polymer (PolyCD). The poorly water-soluble LVB and RD-NO solubilize very well within the polymeric host leading to a ternary supramolecular nanoassembly with a diameter of ~55 nm. The efficiency of the NO photorelease and the typical red fluorescence of RD-NO significantly enhance within the polymer due to its active role in the photochemical and photophysical deactivation pathways. The co-presence of LVB within the same host does not affect either the nature or the efficiency of the photoinduced processes of RD-NO. Besides, irradiation of RD-NO does not lead to the decomposition of LVB, ruling out any intermolecular photoinduced process between the two guests despite sharing the same host. Ad-hoc devised Förster Resonance Energy Transfer experiments demonstrate this to be the result of the not close proximity of the two guests, which are confined in different compartments of the same polymeric host. The supramolecular complex is stable in a culture medium, and its biological activity has been evaluated against HEP-G2 hepatocarcinoma cell lines in the dark and under irradiation with visible green light, using LVB at a concentration well below the IC50. Comparative experiments performed using the polymeric host encapsulating the individual LVB and RD-NO components under the same experimental conditions show that the moderate cell mortality induced by the ternary complex in the dark increases significantly upon irradiation with visible green light, more likely as the result of synergism between the NO photogenerated and the chemotherapeutic

Photocatalytic degradation of methylene blue at nanostructured ZnO thin films

The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l−1 MB solution, 540 minUV irradiation), the rate constant k of MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10–9 (mol·l−1·min−1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB

Synthesis, characterization and photocatalytic properties of nanostructured lanthanide doped β-NaYF4/TiO2 composite films

The photocatalytic approach is known to be one of the most promising advanced oxidation processes for the tertiary treatment of polluted water. In this paper, beta-NaYF4/TiO2 composite films have been synthetized through a novel sol-gel/spin-coating approach using a mixture of beta-diketonate complexes of Na and Y, and Yb3+, Tm3+, Gd3+, Eu3+ as doping ions, together with the TiO2 P25 nanoparticles. The herein pioneering approach represents an easy, straightforward and industrially appealing method for the fabrication of doped beta-NaYF4/TiO2 composites. The effect of the doped beta-NaYF4 phase on the photocatalytic activity of TiO2 for the degradation of methylene blue (MB) has been deeply investigated. In particular, the upconverting TiO2/beta-NaYF4: 20%Yb, 2% Gd, x% Tm (x = 0.5 and 1%) and the downshifting TiO2/beta-NaYF4: 10% Eu composite films have been tested on MB degradation both under UV and visible light irradiation. An improvement up to 42.4% in the degradation of MB has been observed for the TiO2/beta-NaYF4: 10% Eu system after 240 min of UV irradiation

Solar-driven photodegradation of ciprofloxacin and E. coli growth inhibition using a Tm3+ upconverting nanoparticle-based polymer composite

Solar-driven photocatalysis is of great interest in terms of a sustainable use of energy and its application in wastewater treatment. The UV light-driven photogeneration of H2O2 by solar irradiation is an advanced strategy for the treatment of bacteria and recalcitrant pollutants in wastewater, but suffers from low efficiencies. In this work, a solar-driven multifunctional nanocomposite consisting of Tm3+ upconverting nanoparticles, poly(vinyl alcohol), poly(acrylic acid) and hydroxylated sulfonated poly(ether ether ketone) was prepared. The components were crosslinked via a heating treatment at 170 °C, resulting in a non-leaching porous material. This nanocomposite exhibited excellent adsorption ability (89 % in 150 min) toward a 100 mg/L ciprofloxacin aqueous solution and proved to photodegrade it (50 %) upon 4 h artificial solar irradiation, exploiting photon upconversion processes. Moreover, an 80 % bactericidal effect against E. coli was registered upon sunlight irradiation. Altogether, these results suggest the feasibility of a solar-driven wastewater treatment based on upconverting nanoparticles