Successful application of photocatalytic recycled TiO2-GO membranes for the removal of trace organic compounds from tertiary effluent.

Photocatalytic membranes are a promising technology for water and wastewater treatment. Towards circular economy, extending the lifetime of reverse osmosis (RO) membranes for as long as possible is extremely important, due to the great amount of RO modules discarded every year around the world. Therefore, in the present study, photocatalytic membranes made of recycled post-lifespan RO membrane (polyamide thin-film composite), TiO2 nanoparticles and graphene oxide are used in the treatment tertiary-treated domestic wastewater to remove trace organic compounds (TrOCs). The inclusion of dopamine throughout the surface modification process enhanced the stability of the membranes to be used as long as 10 months of operation. We investigated TrOCs removal by the membrane itself and in combination with UV-C and visible light by LED. The best results were obtained with integrated membrane UV-C system at pH 9, with considerable reductions of diclofenac (92%) and antipyrine (87%). Changes in effluent pH demonstrated an improvement in the attenuation of TrOCs concentration at higher pHs. By modifying membranes with nanocomposites, an increase in membrane hydrophilicity (4° contact angle reduction) was demonstrated. The effect of the lamp position on the light fluence that reaches the membrane was assessed, and greater values were found in the middle of the membrane, providing parameters for process optimization (0.29 ± 0.10 mW cm-2 at the center of the membrane and 0.07 ± 0.03 mW cm-2 at the right and left extremities). Photocatalytic recycled TiO2-GO membranes have shown great performance to remove TrOCs and extend membrane lifespan, as sustainable technology to treat wastewater.

Converting recycled membranes into photocatalytic membranes using greener TiO2-GRAPHENE oxide nanomaterials.

Despite the widespread use of membrane separation processes for water treatment, operation costs and fouling still restrict their application. Costs can be overcome by recycled membranes whereas fouling can be mitigated by membrane modification. In this work, the performance of recycled reverse osmosis membranes modified by greener titanium dioxide (TiO2) and graphene oxide (GO) in different modification routes were investigated and compared. The use of recycled membranes as a support acted more than a strategy for costs reduction, but also as an alternative for solid waste reduction. Low adhesion of nanoparticulate materials to the membrane surfaces were verified in depositions by self-assembly, whereas filtration and modification with dopamine generated membranes with well adhered and homogeneous layers. Considering the stability, permeability, and rejection efficiency of dyes as model substrates, the membranes modified with the aid of dopamine-TiO2-GO were the most promising. The nanomaterials increased the membrane hydrophilicity and formed a hydrated layer that repels the organic contaminants and reduces fouling. Besides membrane rejection, adsorption (contribution: ∼10%) and photocatalysis (contribution: ∼20%) were additional mechanisms for pollutants removal by the modified membranes. The photocatalytic membrane modified with dopamine-TiO2-GO was furthermore evaluated for the removal of six different pharmaceutical active compounds (PhACs), noticing gains in terms of removal efficiency (up to 95.7%) and fouling mitigation for the modified membrane compared to the original membranes. The photocatalytic activity still contributed to a simultaneous degradation of PhACs avoiding the generation of a concentrated stream for further disposal.

Ag/GO/TiO2nanocomposites: the role of the interfacial charge transfer for application in photocatalysis.

TiO2semiconductor nanoparticles (NPs) in the anatase phase have presented limitations of application in photocatalysis, mainly due to the fast recombination of photoexcited electrons. The combination with other nanoparticles/nanostructures has been shown to be a promising solution for increasing photocatalytic efficiency. In this work, titanium dioxide (TiO2) nanoparticles in different crystalline phases were prepared through a rapid microwave-assisted synthesis and modified by silver nanoparticles (Ag) and graphene oxide (GO). The samples were characterized by x-ray diffraction, transmission electron microscopy, energy dispersive x-ray spectroscopy, infrared spectroscopy and gas adsorption. Crystalline anatase NPs were obtained in basic conditions (pH = 8) while in acidic conditions (pH = 1), single-crystalline rutile NPs were formed. Different previous drying methods: oven and freeze-drying used led to a differentiation in crystallographic phases obtained. Anatase TiO2and anatase-rutile mixture NPs calcined at 400 °C showed properties as high specific surface area, crystallinity and reduced electron-hole recombination which contributed to an enhanced photocatalytic activity, when compared to the Degussa P25 photoactivity. The effect of silver nanoparticles and GO addition to TiO2nanopowder was evaluated for photocatalysis activity. An improvement in the methylene blue and rhodamine B dyes photodegradation was observed for both anatase and rutile TiO2nanocomposites. We noted that anatase TiO2nanoparticles degraded 53% of rhodamine B, and when functionalized with GO, the photodegradation increased to 69%. Comparatively, the addition of silver nanoparticles to anatase TiO2increased the dye degradation to 97% in 180 min. Hence, we revel that in the TiO2nanocomposites, silver nanoparticles showed better interfacial charge transfer than GO, contributing more effectively to the dye photodegradation process.

Graphene oxide in the remediation of norfloxacin from aqueous matrix: simultaneous adsorption and degradation process.

In the present study, the simultaneous adsorption degradation of norfloxacin (NOR) by graphene oxide from aqueous matrix was verified. Graphene oxide (GO, ~ 8 layers) was prepared using modified Hummers method through the oxidation/exfoliation of expanded graphite. Spectroscopic techniques confirmed the NOR adsorption onto GO surface and the partial antibiotic degradation promoted by hydroxyl radicals derived from GO. Furthermore, the mass spectra after the adsorption-degradation processes showed NOR degradation intermediates that was compared and confirmed by other studies. The nanomaterial showed a removal capacity of 374.9 ± 29.8 mg g-1, observing greater contribution from the NOR in the zwitterionic form and removals up to 94.8%. The intraparticle diffusion process, assessed by Boyd's model and Fick's law, presented a greater contribution in the removal process, reaching the equilibrium 30 min after the beginning. In addition, the temperature increase would disadvantage the process, which was considered thermodynamically viable throughout the evaluated temperature range. Finally, the process was scaled-up in a single stage batch adsorber considering a NOR removal efficiency of 95%. This resulted in mass requirement of 63.6 g of GO in order to treat 0.5 m3 of contaminated water. In general, the simultaneous adsorption-degradation process was considered innovative and promising in pharmaceutical compounds remediation.

Bismuth sulphides prepared by thermal and hydrothermal decomposition of a single source precursor: the effect of reaction parameters on morphology, microstructure and catalytic activity.

Bismuth sulphides were prepared by thermal and hydrothermal decomposition of a precursor, bismuth tris-diethyldithiocarbamate, at different temperatures and times. The obtained results showed that the thermal decomposition of the precursor in a tube furnace was not very appropriate to control particle size and morphology. XRD results showed that at 310 °C the precursor was not fully decomposed but at 500 °C besides the orthorhombic bismuth sulphide, the metallic bismuth also started to be formed. At the highest temperature 1D crystals were formed with an apparent mean crystal size of 138 nm. However, hydrothermal decomposition was shown to be a very suitable method to control particle size and morphology just by varying some parameters such as temperature and time. For 6 hours reaction time, as temperature increased, the apparent mean crystal size decreased. The particle morphology was also very affected by this parameter, at 180 °C only 1D particles (nanorods) with lengths varying from 25 to 4700 nm were formed but at 200 °C not only 1D particles but also 2D particles were (nanosheets) obtained. Bismuth sulphide particles obtained at 180 °C and 24 hours reaction time were shown to be formed mostly by 2D particles compared to those obtained at 6 hours. It was clearly seen that the increase in reaction time and temperature led to the formation of bi-dimensional particles. The presence of 1D crystals in the samples obtained by hydrothermal decomposition at 180 °C/6 h and 180 °C/24 h is responsible for their high catalytic efficiency towards methylene blue dye degradation.