Materiais para a Energia - ME
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Browsing Materiais para a Energia - ME by Sustainable Development Goals (SDG) "07:Energias Renováveis e Acessíveis"
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- Detection of corrosion on silvered glass reflectors via image processingPublication . Wiesinger, Florian; Baghouil, Sarah; Le Baron, Estelle; Collignon, Romain; Santos, Filipa; Cunha Diamantino, Teresa; Catarino, Isabel; Facão, Jorge; Ferreira, Cristina; Páscoa, Soraia; Sutter, Florian; Fernández-García, Aránzazu; Wette, JohannesABSTRACT: A novel characterization technique based on image analysis is presented, intended to complement state-of-the-art reflectometer measurements. The technique is developed by experts from different laboratories (OPAC, AGC, CEA and LNEG), which subsequently conduct two Round Robin experiments on corroded solar reflectors for validation. Regarding the inter-comparability, it is found that parameters like the corrosion spot density or the penetration maximum on coated edges exhibit an average coefficient of variation of 62.6 % and 54.9 %. Better agreement is found for parameters like the total corroded area and the maximum edge corrosion penetration, with coefficients of variation of 14.3 % and 13.4 %, respectively. The developed methodology is further applied during a 68-month lasting outdoor exposure campaign of two types of solar reflectors at two representative sites, one exhibiting corrosivity class C2 and the other C3. On the commercial coating RL1, a total corroded area of 59 mm2 and 426 mm2 is measured after the outdoor exposure on the C2 and the C3 site, respectively, while on the novel low-lead coated reflector RL3 corresponding values are 280 mm2 and 1308 mm2. This shows the superior quality of the coating RL1 in terms of corrosion resistance. Furthermore, the analysis highlights the importance of proper edge sealing for corrosion protection, since corrosion penetration is increased by a factor between 1.3 and 4.0 if the edges are unprotected. The reflectance decrease after the outdoor exposure is regarded as negligible (0.000 - 0.005), thus not permitting any of the conclusions that are made from the novel image analysis technique.
- Evolution of atomically dispersed co-catalysts during solar or UV photocatalysis for efficient and sustained H2 productionPublication . Capelo, Anabela; Fattoruso, Domenico; Valencia-Valero, Laura; Esteves, M. Alexandra; Rangel, Carmen M.; Puga, AlbertoABSTRACT: The evolution of metal/titania photocatalysts during photocatalytic H-2 evolution is herein studied. Samples containing atomically dispersed Pt co-catalysts (single atoms, clusters and sub-nanoparticles) formed after calcination were compared to pre-reduced analogues mostly having metallic nanoparticles (diameters >1 nm) during ethanol photoreforming under either UV-rich irradiation or natural sunlight. Aggregation of ultra-dispersed oxidised platinum entities (Pt delta+) with concomitant reduction into Pt-0 nanoparticles (1-2 nm) was observed after UV irradiation by transmission electron microscopy (TEM), and diffuse reflectance UV-visible (DRUV-vis) and X-ray photoelectron (XPS) spectroscopies. A parallel, albeit slower, evolution trend was evidenced during solar photocatalysis. Conversely, atomically dispersed Cu co-catalyst species did not grow and became in-situ reduced into sub-nanometric Cu-0 under irradiation. Hydrogen production rates were remarkably high during initial stages of UV irradiation, and then declined to a sustained regime (approximate to 50 and 8 mmol g(-1) h(-1) for Pt/TiO2 or Cu/TiO2, respectively, for up to 24 h of irradiation). Steadier solar photoreforming was observed in experiments performed in a compound parabolic collector tubular reactor (approximate to 7.6 and 1.7 mmol g(-1) h(-1) for Pt/TiO2 or Cu/TiO2, respectively). Despite the non-negligible effect of co-catalyst rearrangement on activity rationalised herein, attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy measurements pre- and post-photocatalysis suggest that accumulation of strongly adsorbed degradation intermediates, chiefly acetate, is a major cause for rate decreases. Notwithstanding, this phenomenon did not result in total deactivation, so that sustained hydrogen production upon long-term irradiation was not compromised.
- The H2Excellence Project-Fuel Cells and Green Hydrogen Centers of Vocational Excellence Towards Achieving Affordable, Secure, and Sustainable Energy for EuropePublication . Gano, António; Ribeiro Pinto, Paulo Jorge; Esteves, M. Alexandra; Rangel, Carmen M.ABSTRACT: The demand for green hydrogen (H2) and related technologies is expected to increase in the coming years, driven by climate changes and energy security of supply issues, amid the European and global energy crises. The European Green Deal and REpowerEU Plan have identified H2 as a key pillar for reaching climate neutrality by 2050 and for the intensification of hydrogen delivery targets, bringing the large-scale adoption of hydrogen production and applications, and stressing the need for a skilled workforce in emergent H2 markets. To that end, the H2Excellence project will establish a Platform of Vocational Excellence in the field of fuel cells and green hydrogen technologies, with an educational and training scheme to tackle identified skill gaps and to implement life-long learning opportunities. This project aims to become a European benchmark in training and knowledge transfer, incorporating the entire hydrogen value chain. The work is supported by the Knowledge Triangle Model, integrating education, research, and innovation efforts to build a dynamic ecosystem in the green hydrogen sector. In this work, activities conducted so far by LNEG as a project partner and expected impacts are highlighted. Those activities are based on a stakeholder needs assessment conducted by project partners and on the knowledge and experience accumulated in research activities developed in the Materials for Energy research area.
- Mechanical Performance of Ceria-Coated 3D-Printed Black Zirconia Cellular Structures After Solar Thermochemical CO/H2 Fuel Production CyclesPublication . Oliveira, Fernando; Sardinha, Manuel; Justino Netto, Joaquim Manoel; Leite, Marco; Farinha, Miguel; Barreiros, Maria Alexandra; Abanades, Stéphane; Fernandes, JorgeABSTRACT: Solar fuels production requires developing redox active materials with porous structures able to withstand thermochemical cycles with enhanced thermal stability under concentrated solar irradiation conditions. The mechanical performance of 3D-printed, macroporous black zirconia gyroid structures, coated with redox-active ceria, was assessed for their suitability in solar thermochemical cycles for CO2 and H2O splitting. Experiments were conducted using a 1.5 kW solar furnace to supply the high-temperature concentrated heat to a windowed reaction chamber to carry out thermal redox cycling under realistic on-sun conditions. The ceria coating on ceramic structures improved the thermal stability and redox efficiency while minimizing the quantity of the redox material involved. Crushing strength measurements showed that samples not directly exposed to the concentrated solar flux retained their mechanical performance after thermal cycling (similar to 10 MPa), while those near the concentrated solar beam focus exhibited significant degradation due to thermal stresses and the formation of CexZr1-xO2 solid solutions (similar to 1.5 MPa). A Weibull modulus of 8.5 was estimated, marking the first report of such a parameter for fused filament fabrication (FFF)-manufactured black zirconia with gyroid architecture. Failure occurred via a damage accumulation mechanism at both micro- and macro-scales. These findings support the viability of ceria-coated cellular ceramics for scalable solar fuel production and highlight the need for optimized reactor designs.
- New Modified SPEEK-Based Proton Exchange MembranesPublication . Teixeira, Fatima; Teixeira, António Paulo Silva; Rangel, Carmen M.ABSTRACT: A decarbonized society demands cleaner and sustainable energy sources based on well-established or emerging technologies with the potential to make a significant contribution to energy storage and conversion, such as batteries, fuel cells and water and/or CO2 electrolyzers. The performance of these electrochemical devices relies on key components such as their separators/ion-exchange membranes. The most common commercial membrane, Nafion (R), has several technological limitations. In this study, it is proposed the incorporation of bisphosphonic acid (BP) dopants into membrane matrices to improve their properties. Following this strategy, we prepared new membranes based on sulfonated poly(etheretherketone) (SPEEK) polymer, a reliable and effective alternative membrane polymer, through the incorporation of the BP dopants, to obtain low-cost membranes with improved properties. These membranes were structural, thermal and morphological, characterized by AT-FTIR, TGA and SEM. Their proton conductivity was evaluated over a temperature range between 30 degrees C and 60 degrees C, using Electrochemical Impedance Spectroscopy, and their stability during this process was also observed. The best proton conductivity was observed for the SPEEK membrane doped with BP1 at 2.0 wt% load at 60 degrees C, with a proton conduction of 226 mS cm-1.
- New proton exchange membranes based on ionic liquid doped chitosanPublication . Naffati, Naima; Teixeira, Fatima; Teixeira, António Paulo Silva; Rangel, Carmen M.ABSTRACT: The development of new proton exchange membranes (PEM) for electrochemical devices have attracted researcher's attention in the pursuit for more sustainable and cost-effective technologies for clean energy production and conversion. In this work, new doped chitosan (CS) membranes were prepared by the casting method. Chitosan is an abundant, biodegradable and non-toxic material, and as a membrane, a sustainable and cheaper alternative to those perfluorinated and commonly used, such as Nafion. Three different ionic liquids were employed as dopants, ([EMIM][OTf], [EMIM][FSI] and [MIMH][HSO4]), in various concentrations and up to 50 wt% load. The new membranes were characterized by ATR-FTIR, thermogravimetry, using TGA and DSC techniques to assess their thermal properties, and by SEM, to analyse their surface morphology. Proton conduction properties of the new membranes were assessed by Electrochemical Impedance Spectroscopy (EIS). The new doped membranes showed an increase in the proton conduction compared with pristine chitosan membranes. The incorporation of ionic liquids into chitosan membranes improved their proton conductivity and thermal properties, with [EMIM][OTf] and [MIMH][HSO4] showing the most promising results. A 2-fold increment in the proton conduction was generally observed with the increase of the temperature from 30 to 60 degrees C. The best proton conductivity was found at 60 degrees C for the membrane doped with [EMIM][OTf], with a value of 47 mS.cm(-1).
- Scale-up of a clean hydrogen production system through the hydrolysis of sodium borohydride for off-grid applicationsPublication . Silva, Diogo; Nunes, Helder Xavier; Rangel, Carmen M.; Pinto, A. M. F. R.ABSTRACT: Hydrogen is considered a promising energy vector with the potential to replace fossil fuels, and sodium borohydride serves as an effective energy carrier capable of releasing hydrogen (H2) for off-grid applications. However, the hydrolysis of sodium borohydride has only matured at laboratory-scale. Therefore, the scale-up of a laboratory reactor was designed and manufactured to study the effect of larger H2 production. For that, the effect of inhibitor NaOH concentration and water quality were studied. Experiments using 3 wt% NaOH showed overall better performance than those using 1 wt%. Additionally, experiments using tap water - scarcely reported in the literature - demonstrated performance equal to or better than that achieved with distilled water. These results are indicative of a possible significant reduction in the H2 production cost through this method.
- Simulation of Surface Segregation in Nanoparticles of Pt-Pd AlloysPublication . Correia, Jose B.; Sá, AnaABSTRACT: Platinum (Pt) and palladium (Pd) are crucial in hydrogen energy technologies, especially in fuel cells, due to their high catalytic activity and chemical stability. Pt-Pd nanoparticles, produced through various methods, enhance catalytic performance based on their size, shape, and composition. These nanocatalysts excel in direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs) by promoting alcohol oxidation and reducing CO poisoning. Pt-Pd catalysts are also being explored for their oxygen reduction reaction (ORR) on the cathodic side of fuel cells, showing higher activity and stability than pure platinum. Molecular dynamics (MD) simulations have been conducted to understand the structural and surface energy effects of PdPt nanoparticles, revealing phase separation and chemical ordering, which are critical for optimizing these catalysts. Pd migration to the surface layer in Pt-Pd alloys minimizes the overall potential energy through the formation of Pd surface monolayers and Pt-Pd bonds, leading to a lower surface energy for intermediate compositions compared to that of the pure elements. The potential energy, calculated from MD simulations, increases with a decreasing particle size due to surface creation, indicating higher reactivity for smaller particles. A general contraction of the average distance to the nearest neighbour atoms was determined for the top surface layers within the nanoparticles. This research highlights the significant impact of Pd segregation on the structural and surface energy properties of Pt-Pd nanoparticles. The formation of Pd monolayers and the resulting core-shell structures influence the catalytic activity and stability of these nanoparticles, with smaller particles exhibiting higher surface energy and reactivity. These findings provide insights into the design and optimization of Pt-Pd nanocatalysts for various applications.
- Solar Electrochemical CO2 Reduction to Syngas [Resumo]Publication . Messias, Sofia; Paninho, A. B.; Nunes, Daniela; Rangel, Carmen M.; Nunes, A. V. M.; Branco, Luis; Martins, Rodrigo; Mendes, Manuel Joao; Machado, Ana
- Thermochemical performance of ceria coated-macroporous 3D-printed black zirconia structures for solar CO/H2 fuels productionPublication . Oliveira, Fernando; Barreiros, Maria Alexandra; Sardinha, Manuel; Leite, Marco; Fernandes, Jorge; Abanades, StéphaneABSTRACT: The use of macroporous structured ceria for the solar thermochemical splitting of CO2 and H2O to produce clean fuels through two-step redox cycles was investigated. The research aimed to assess the reactivity of 3D-printed black zirconia gyroid structures coated with a microporous layer of pure CeO2 for producing CO and H2. Such porous designs are intended to increase both the absorption of solar radiation and the available surface area for the solid-gas reaction. It was observed that the structure degraded more at the top of the reactor cavity, where the formation of CexZr1-xO2 solid solutions occurred at the coating/substrate interface. Besides, the porous ceria structure remained after redox cycles in the samples not directly exposed to solar radiation. Consequently, the solar reactor achieved CO and H2 production rates of up to 5.4 and 1.9 mL min-1 g-1 with fuel yield over 0.2 mmol g-1, and the material maintained its performance over several consecutive cycles without any loss of reactivity. This indicates a strong potential for producing solar fuels at a large facility using custom 3D-printed ceria-coated structures.