Sónia Fernandes

Abstract The effectiveness of various transition metal phosphate-based acid catalysts, including vanadium and niobium, in the hydrothermal synthesis of carbon dots (CDs), has been assessed. Two sources of carbohydrates were employed for this: commercial xylose and liquor of xylose produced by processing olive pits. Catalysts were identified using the NH3-TPD, DTA/TG, XRD, and XPS techniques. The reaction was conducted for 4 h at a temperature of 180 degrees C. The existence of such nanoparticles, regardless of the carbohydrate source, was confirmed by an analysis of the features and characteristics of CDs nanoparticles. N-doped CDs with increased fluorescence were also created at the same time using a similar hydrothermal technique, and their photocatalytic activity was investigated. A Life Cycle Assessment (LCA) was conducted for both syntheses with the goal of comparing the environmental effects of the synthesis from commercial xylose to the synthesis from biomass. It was revealed that, although energy is the primary driver of both synthesis pathways' effect categories, the fundamental variations that seem to determine their relative sustainability are connected to the nature of the carbon precursor. Regarding the latter, it is determined that electricity has the greatest environmental impact.

Abstract A sustainable matrix based on eucalyptol essential oil/sawdust was developed and applied on laminated plywood. This finish aims to serve as a eucalyptol odor slow release. Eucalyptol odor release was monitored with gas chromatography coupled with a flame ionization detector (GC-FID: Limits of Detection and Quantification of 0.70 g/m3 and 2.11 g/m3, respectively, and with linearity up to 18.6 g/m3). Measurement of the eucalyptol odor released was performed during a six-month period, and it was found that the release followed a first-order exponential decay with a decay rate constant of 0.0169 per day. The half-life was determined to be of 48 days. The granulometry and particle size porosity of sawdust were analyzed by Scanning Electron Microscopy. A sawdust size fraction of 112-200 mu m showed the best eucalyptol absorption capacity, with 1:3 masses ratio (sawdust:eucalyptol). The release duration of eucalyptol is influenced by the quantity of the eucalyptol-sawdust composite and the aperture size for release. Through the determination of this relationship, it was found that applying 15.0 g of the composite through a 0.8 mm diameter aperture resulted in a 6-month eucalyptol release period. This outcome is regarded as highly favorable, considering the inherent high volatility of eucalyptol and the relatively small amount of composite required for future product applications. The new product is characterized by a carbon footprint (considering the industry frontiers) of 5.94 kg CO2eq/m2 of plywood floor.

Abstract Carbon dots (CDs) are carbon-based nanomaterials with remarkable properties that can be produced from a wide variety of synthesis routes. Given that standard bottom-up procedures are typically associated with low synthesis yields, different authors have been trying to devise alternative high-yield fabrication strategies. However, there is a doubt if sustainability-wise, the latter should be really preferred to the former. Herein, we employed a Life Cycle Assessment (LCA) approach to compare and understand the environmental impacts of high-yield and standard bottom-up strategies, by applying different life cycle impact assessment (LCIA) methods. These routes were: (1) production of hydrochar, via the hydrothermal treatment of carbon precursors, and its alkaline peroxide treatment into high-yield CDs; (2) microwave treatment of carbon precursors doped with ethylenediamine; (3) and (6) thermal treatment of carbon precursor and urea; (4) hydrothermal treatment of carbon precursor and urea; (5) microwave treatment of carbon precursor and urea. For this LCA, four LCIA methods were used: ReCiPe, Greenhouse Gas Protocol, AWARE, and USEtox. Results identified CD-5 as the most sustainable synthesis in ReCiPe, Greenhouse Gas Protocol, and USEtox. On the other hand, in AWARE, the most sustainable synthesis was CD-1. It was possible to conclude that, in general, high-yield synthesis (CD-1) was not more sustainable than standard bottom-up synthesis, such as CD-5 and CD-6 (also with relatively high-yield). More importantly, high-yield synthesis (CD-1) did not generate much lower environmental impacts than standard approaches with low yields, which indicates that higher yields come with relevant environmental costs.

Abstract Carbon dots (CDs) are carbon-based nanomaterials with advantageous luminescent properties, making them promising alternatives to other molecular and nanosized fluorophores. However, the development of CDs is impaired by the low synthesis yield of standard fabrication strategies, making high-yield strategies essential. To help future studies to focus on cleaner production strategies, we have employed a Life Cycle Assessment (LCA) to compare and understand the environmental impacts of available routes for the high-yield synthesis of carbon dots. These routes were: (1) production of hydrochar, via hydrothermal treatment of carbon precursors, and its alkaline-peroxide treatment into high-yield carbon dots; (2) thermal treatment of carbon precursors mixed in a eutectic mixture of salts. Results show that the first synthesis route is associated with the lowest environmental impacts. This is attributed to the absence of the mixture of salts in the first synthesis route, which offsets its higher electricity consumption. Sensitivity analysis showed that the most critical parameter in the different synthetic strategies is the identity of the carbon precursor, with electricity being also relevant for the first synthesis route. Nevertheless, the use of some carbon precursors (as citric acid) with higher associated environmental impacts may be justified by their beneficial role in increasing the luminescent performance of carbon dots. Thus, the first synthesis route is indicated to be the most environmental benign and should be used as a basis in future studies aimed to the cleaner and high-yield production of carbon dots.

Abstract While TiO2 nanoparticles have shown potential as photocatalysts in the degradation of organic contaminants, their inability to absorb efficiently visible light has limited their industrial application. One strategy for solving this problem is monodoping TiO2 photocatalysts with transition metals, which has worked in the degradation of several pollutants. However, it is not clear if this improvement is enough to offset the potential environmental impacts of adding metal ions to the synthesis of TiO2. Herein, we have used Life Cycle Assessment (LCA) to determine the sustainability of monodoping TiO2 with transition metals (Fe, Co, Mn and Ni, with a 1% weight ratio) to enhance the photocatalytic properties of the photocatalyst toward the degradation of Carbamazepine and Methyl Orange, under UV-A and visible light irradiation. We found that the addition of transition-metals has no significant effect on the environmental impacts associated with the synthesis of TiO2, when a weight-based functional unit was considered. However, when photocatalytic activity was considered, major differences were found. Thus, our results demonstrate that the sustainability of monodoping with different transition metals is solely determined by their ability to enhance (or not) the photocatalytic activity of TiO2. Our data also demonstrated that isopropyl alcohol constitutes a critical point in the synthesis of TiO2 photocatalysts, with ethanol being a potential substitute.