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- 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.
- Modification of MOR by desilication treatments: structural, textural and acidic characterizationPublication . Paixão, Viviana; Carvalho, Ana P.; Rocha, João; Fernandes, Auguste; Martins, AngelaThe effect of several desilication experimental parameters (base concentration, temperature and time) on the characteristics of MOR zeolite was studied. The samples were characterized by X-ray diffraction, Al-27 and Si-29 MAS-NMR, chemical analysis, and FTIR (framework vibration region). The textural characterization was made by N-2 adsorption and the acidity was evaluated by pyridine adsorption followed by FTIR and by the catalytic model reaction of n-heptane cracking. The alkaline treatments promoted the Si extraction from the zeolite framework, without considerable loss of crystallinity and, as it was envisaged, an important increase of the mesoporous structure was attained. A linear correlation between the number of framework Si per unit cell. N-Si and the asymmetric stretching wavenumber, nu(i), was observed. The acidity characterization shows that the desilicated samples exhibit practically the same acid properties than the parent HMOR zeolite. The optimum desilication conditions were those used to obtain sample M/0.2/85/2, i.e., sample treated with 0.2 M NaOH solution at 85 degrees C for 2 h.
- Zooming in with QSPR on Friedel-Crafts acylation reactions over modified BEA zeolitesPublication . Aleixo, Odrigo; Elvas Leitao, Ruben; Martins, Filomena; Carvalho, Ana; Brigas, Amadeu Fernandes; Nunes, Ricardo; Fernandes, Auguste; Rocha, Joao; Martins, Angela; Nunes, NelsonThe catalytic behaviour of hierarchical BEA zeolites with Si/Al ratio of 12.5 and 32 was studied in Friedel-Crafts acylation reactions using furan, anisole and pyrrole as substrates and acetic anhydride as acylating agent. Hierarchical BEA samples were submitted to alkaline and alkaline + acid treatments. Kinetic modelling using nonlinear regressions applied to a simplified Langmuir-Hinshelwood equation showed that the Si/Al ratio of the parent materials strongly influenced the catalytic behaviour. Catalytic results were correlated with physicochemical properties using a Quantitative Structure-Property Relationship (QSPR) methodology. This approach provided detailed information about the role of key properties on the catalytic behaviour, and pointed out which properties should be modified through direct synthesis and/or post-synthesis treatments to obtain materials with optimized catalytic performance.
- Zeolites and related materials as catalyst supports for hydrocarbon oxidation reactionsPublication . Martins, Angela; Nunes, Nelson; Carvalho, Ana P.; Martins, LuisaCatalytic oxidation is a key technology for the conversion of petroleum-based feedstocks into useful chemicals (e.g., adipic acid, caprolactam, glycols, acrylates, and vinyl acetate) since this chemical transformation is always involved in synthesis processes. Millions of tons of these compounds are annually produced worldwide and find applications in all areas of chemical industries, ranging from pharmaceutical to large-scale commodities. The traditional industrial methods to produce large amounts of those compounds involve over-stoichiometric quantities of toxic inorganic reactants and homogeneous catalysts that operate at high temperature, originating large amounts of effluents, often leading to expensive downstream processes, along with nonrecovery of valuable catalysts that are loss within the reactant effluent. Due to the increasingly stringent environmental legislation nowadays, there is considerable pressure to replace these antiquate technologies, focusing on heterogeneous catalysts that can operate under mild reactions conditions, easily recovered, and reused. Parallelly, recent advances in the synthesis and characterization of metal complexes and metal clusters on support surfaces have brought new insights to catalysis and highlight ways to systematic catalysts design. This review aims to provide a comprehensive bibliographic examination over the last 10 years on the development of heterogeneous catalysts, i.e., organometallic complexes or metal clusters immobilized in distinct inorganic supports such as zeolites, hierarchical zeolites, silicas, and clays. The methodologies used to prepare and/or modify the supports are critically reviewed, as well as the methods used for the immobilization of the active species. The applications of the heterogenized catalysts are presented, and some case-studies are discussed in detail.
- 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.
- Probing substrate/catalyst effects using QSPR analysis on friedel-crafts acylation reactions over hierarchical BEA zeolitesPublication . Elvas Leitao, Ruben; Martins, Filomena; Borbinha, Leonor; Marranita, Catarina; Martins, Angela; Nunes, NelsonAttempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates' molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.
- 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.
- 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.
- 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.
- 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.