Browsing by Author "Nunes, Nelson"
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- Adsorption of a textile dye on commercial activated carbon: a simple experiment to explore the role of surface chemistry and ionic strengthPublication . Martins, Angela; Nunes, NelsonIn this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water hardness. The purpose of this experimental work, directed to undergraduate (second-year) students is to allow them to understand the influence of surface chemistry and ionic strength on the interaction between the carbon surface and the dye molecule.
- Biomass-derived nanoporous carbons as electrocatalysts for oxygen reduction reactionPublication . Fernandes, Diana M; Mestre, Ana S.; Martins, Angela; Nunes, Nelson; Carvalho, A. P.; Freire, CristinaElectrocatalysts (ECs) for the oxygen reduction reaction (ORR) are crucial in fuel cells and for this reason developing cost-effective metal-free ECs with high electrocatalytic activity and high-volume production remains a huge challenge. Herein, we report the application as ORR electrocatalysts of a series of high grade nanoporous carbons, prepared by chemical activation of acid-chars obtained from the H2SO4 digestion and polycondensation (acid-mediated carbonization) of a biomass residue (Agave sisalana). All the nanoporous carbons presented good ORR electrocatalytic activities in alkaline medium. The AC(1) carbon exhibited the most promising ORR performance with E-onset = 0.84 vs. RHE, j(L, 0.26 V, 1600 rpm) = -3.12 mA cm(-2) and n(O2) = 3.6 electrons. The Tafel slopes of all carbons varied between 47 mV dec(-1) (AC(3)) and 250 mV dec(-1) (AC(1)). Furthermore, the carbons revealed superior tolerance to methanol when compared with commercial Pt/C and a competitive long-term electrochemical stability, with current retentions of 75-85 % after 20,000 s. The results obtained in this work suggest a promising method based on sustainable and economical biomass residues towards the development and engineering of novel value-added biomass-derived carbons as effective metal-free electrocatalysts for alkaline fuel cells.
- Coal fly ash waste, a low-cost adsorbent for the removal of Mordant Orange dye from aqueous mediaPublication . Rosa, Teresa; Martins, Angela; Santos, Maria Teresa; Trindade, Teodoro; Nunes, NelsonIn this study, a coal fly ash material generated in a Portuguese coal thermal powerplant was tested as a low-cost adsorbent to remove dye molecules. Pre-treatment of the coal fly ash samples was not performed in order to reduce end use cost. Physical and chemical characterization revealed their inert nature and low effects lixiviation in aqueous media. Preliminary adsorption studies include adsorbent quantity, and adsorption kinetics. The adsorption studies focused on Mordant Orange 1 (Mo1) dye, but two other molecules, Rhodamine B (RhB) and Methylene Blue (MeB) were also included for comparison reasons. The adsorption isotherms were tested with different models including Langmuir, Freundlich and modified Langmuir-Freundlich. The effect of temperature, pH and unburn carbon in the adsorption process were also studied. The results show that adsorption capacity of the coal fly ash occurs mainly due to electroestatic interactions between the adsorbent surface and the adsorbate, which depends on the pH of the aqueous media and the surface chemistry of the material, quantified by the point of zero charge, pHpzc. These joint effects are responsible for the higher retention of Mo1 that is about 16 times higher, when compared to the other two molecules tested.
- Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrenePublication . Silva, Ana R.; Guimaraes, Vanessa; Carneiro, Liliana; Nunes, Nelson; Borges, Susana; Pires, Joao; Martins, Angela; Carvalho, Ana P.A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.
- Densities and refractive indices for the ternary mixture methanol/propan-1-Ol/acetonitrilePublication . Elvas Leitao, Ruben; Martins, Filomena; Ventura, M. Cristina; Pinheiro, Lídia; Nunes, NelsonRefractive indices, n(D), and densities, rho, at 298.15 K were measured for the ternary mixture methanol (MeOH)/propan-1-ol (1-PrOH)/acetonitrile (MeCN) for a total of 22 mole fractions, along with 18 mole fractions of each of the corresponding binary mixtures, methanol/propan-1-ol, propan-1-ol/acetonitrile and methanol/acetonitrile. The variation of excess refractive indices and excess molar volumes with composition was modeled by the Redlich-Kister polynomial function in the case of binary mixtures and by the Cibulka equation for the ternary mixture. A thermodynamic approach to excess refractive indices, recently proposed by other authors, was applied for the first time to ternary liquid mixtures. Structural effects were identified and interpreted both in the binary and ternary systems. A complex relationship between excess refractive indices and excess molar volumes was identified, revealing all four possible sign combinations between these two properties. Structuring of the mixtures was also discussed on the basis of partial molar volumes of the binary and ternary mixtures.
- Exploring the effect of hierarchical porosity in BEA zeolite in Friedel-Crafts acylation of furan and benzofuranPublication . Nunes, Nelson; Carvalho, Ana P.; Elvas Leitao, Ruben; Martins, Filomena; Fernandes, Auguste; Rocha, João; Martins, AngelaHierarchical BEA zeolite was prepared through desilication or desilication followed by acid treatment. The catalytic performance of BEA zeolite samples was evaluated using Friedel-Crafts acylations with two substrates of different molecular sizes, furan (5.7 Å) and benzofuran (6.9 Å), in the presence of acetic anhydride as acylating agent. The application of the simplified Langmuir Hinshelwood kinetic model showed that the size of the substrate leads to different catalytic activities, with improved rate constant and turnover frequency (TOF) solely in the presence of benzofuran for both desilicated and further acid treated samples. The mesopores developed during the zeolite treatments have an important role as transportation channels by reducing diffusion limitations. The application of Quantitative Structure–Property Relationships (QSPR) allowed the finding of the most relevant properties of the zeolite and substrate with impact on the catalytic parameters.
- Friedel-crafts acylation reaction over hierarchical Y zeolite modified through surfactant mediated technologyPublication . Martins, Angela; Neves, Vera; Moutinho, João; Nunes, Nelson; Carvalho, AnaFriedel-Crafts acylation reaction was studied under mild conditions using hierarchical HY zeolite samples prepared through surfactant mediated technology, in the presence of NH4OH, using CTAB or DTAB as surfactants and changing the duration of treatment from 6 to 48 h. The materials were characterized by powder X-ray diffraction, low temperature N2 adsorption isotherms, SEM microscopy and pyridine adsorption followed by FTIR. The catalytic behaviour was studied in the acylation of furan by acetic anhydride. The catalytic results reflect the role of the duration of the treatment as well as the surfactant molecule used. As the time of treatment increases, the enlargement of the pores leads to an increase of the rate constant and turnover frequency (TOF), except for sample modified during longer time, 48 h, due to the occurrence of secondary reactions that produce larger products or reaction intermediates that become trapped inside the pores. The role of the surfactant molecule is also relevant since the sample modified in the presence of the larger surfactant molecule, CTAB, a significant increase in product yield and rate constant is obtained when compared with the sample prepared in the same conditions using DTAB. However, in that case, by prolonging the treatment a substantial decrease in the same parameters occurs due to the occurrence of deactivation phenomena, pointing out that the optimized modification of porosity needs to be customized according to the needs of each catalytic system.
- Hierarchical Zeolites Prepared Using a Surfactant-Mediated Strategy: ZSM-5 vs. Y as Catalysts for Friedel–Crafts Acylation ReactionPublication . Martins, Angela; Amaro, Beatriz; Santos, M. Soledade C. S.; Nunes, Nelson; Elvas Leitao, Ruben; Carvalho, Ana P.Hierarchical ZSM5 and Y zeolites were prepared through a surfactant-mediated strategy with NH4OH changing the duration of the treatment and the amount of CTAB surfactant and taking as reference multiples of the critical micellar concentration (CMC). The materials were characterized using powder X-ray diffraction, N2 adsorption isotherms at -196 degrees C, and SEM and TEM microscopy. The catalytic performance was evaluated in Friedel-Crafts acylation of furan with acetic anhydride at 80 degrees C. The alkaline surfactant-mediated treatment had different effects on the two zeolites. For ZSM5, the CTAB molecular aggregates can hardly diffuse inside the medium-size pores, leading mainly to intercrystalline mesoporosity and increased external surface area, with no positive catalytic impact. On the other hand, for large-pore Y zeolite, the CTAB molecular aggregates can easily diffuse and promote the rearrangement of crystal units around micelles, causing the enlargement of the pores, i.e., intracrystalline porosity. The optimized Y-based sample, treated for 12 h with a CTAB amount 32 times the CMC, shows an increase in product yield and rate constant that was not observed when a higher amount of surfactant was added. The reuse of spent catalysts upon thermal treatment at 400 ◦C shows a regeneration efficiency around 90%, showing good potentialities for the modified catalysts.
- Insights into the thermochemistry of paracetamol in ternary mixtures of eutectic solventsPublication . Lopes, Andreia; Nunes, Nelson; Elvas Leitao, Ruben; Martins, FilomenaSolution enthalpies of paracetamol, ΔsolH, in choline chloride–ethylene glycol–water mixtures were evaluated at 298.15 K. Solvatochromic UV–vis shifts of fve diferent probes (4-nitroaniline, 4-nitroanisole, 4-nitrophenol, N,N-dimethyl-4-nitroani line and 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate) were also assessed for the same mixtures at the same temperature in order to compute the corresponding Kamlet–Taft parameters, α, β, and π*. Quantitative structure–property relationships (QSPR) between ΔsolH and the solvatochromic parameters were established to investigate the solution pro cesses under consideration. Due to the small variability in the solvent parameters, a further set of eight pure solvents were considered. The behavior of paracetamol in eutectic mixtures is shown to be not signifcantly diferent from its behaviour in the pure solvents. The solvents’ basicity measured by β, is the most relevant factor modeling the solution process of this solute in the total set of solvents.
- Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolitesPublication . Aleixo, Rodrigo; Elvas Leitao, Ruben; Martins, Filomena; Carvalho, Ana; Brigas, Amadeu; Martins, Angela; Nunes, NelsonFriedel-Crafts acylation was studied under mild conditions using hierarchical MCM-22 zeolites prepared by desilication and by desilication + acid treatment, using furan, pyrrole and anisole as substrates, and acetic anhydride as acylating agent. Enhanced catalysis was observed for furan and anisole, especially at short reaction times. Kinetic results modelling using non-linear regressions applied to a simplified Langmuir-Hinshelwood equation showed that desilication treatment followed by acid treatment improved kinetics (higher k and TOF). A QSPR methodology using nine substrate and zeolite descriptors was applied to model kinetics and adsorption. For both processes, the best QSPR model equations lead to the same descriptors, namely, Bronsted acidity, as zeolite's feature, and both van der Waals volume and Dimroth-Reichardt E-T(N) parameter (related to dipolarity and Lewis acidity) as substrates' characteristics. Normalization of descriptors allowed quantification of each descriptor's relative importance leading to a better understanding of the catalytic and adsorption processes.