Browsing by Author "Martins, Angela"
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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.
- Ball milling modified SAPO-11 based catalysts for n-Decane hydroisomerizationPublication . Ferreira, Luisa; Ribeiro, Filipa; Fernandes, Auguste; Martins, AngelaBifunctional Pt/SAPO-11 catalysts were prepared using as acid matrix the microporous silico-aluminophosphate, SAPO-11, synthesized under microwave radiation. After synthesis, the material was physically modified using a ball mill, changing the grinding time but keeping frequency constant. The metal function (0.5 wt.% Pt) was introduced through mechanical mixture with commercial Pt loaded alumina. The catalysts were characterized by several techniques: powder X-Ray Diffraction, pyridine adsorption followed by infrared spectroscopy, low temperature N-2 adsorption, Hg intrusion porosimetry and electronic microscopy (SEM). The characterization data show modifications of structural and textural properties of the samples as the milling time increases. The catalytic behaviour of Pt/SAPO-11 materials was studied for hydroisomerization of long chain n-alkanes, using n-decane as model molecule, aiming to increase the production of mono-branched isomers. The catalytic results show that, under optimized milling conditions (60 min; 50 Hz) the selectivity into mono-branched isomers increased when compared with parent catalyst.
- 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 Bis(oxazoline) Encapsulated in Zeolites and Its Application as Heterogeneous Catalysts for the Cyclopropanation of StyrenePublication . Silva, Ana Rosa; Albuquerque, Hélio; Fontes, Andre; Borges, Susana; Martins, Angela; Carvalho, Ana Paula; Pires, JoãoA copper C(2)-symmetric bis(oxazoline), CuBox, was introduced in two forms of commercial Y zeolite: a sodium form (NaY) and an ultrastable form (NaUSY). CuBox was introduced by first partially exchanging the sodium cations of both zeolites for copper and then by refluxing the obtained materials with a solution of bis(oxazoline) (Box). Two different loadings were prepared for each form of zeolite. The materials were characterized by copper ICP-AES, elemental analysis, XPS, FTIR, TG, and nitrogen adsorption isotherms at -196 degrees C. Evidence for Box ligand location in the supercages of NaY and NaUSY zeolites and its coordination to the exchanged copper(II) was obtained by the several techniques used. The materials were all active in the cyclopropanation of styrene with ethyldiazoacetate at room temperature and diastereoselective toward trans cydopropanes. Although the materials containing Box showed low enantioselectivities, their catalytic activities were higher than the parent copper exchanged zeolites, and did not decrease with reuse, at least during three consecutive cycles.
- 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.
- Eco-friendly cyclohexane oxidation by a V-scorpionate complex immobilized at hierarchical MOR zeolitePublication . Ottaviani, Davide; Van-Dúnem, Vanmira; Carvalho, Ana; Martins, Angela; Martins, LuisaThe hydrotris(3,5-dimethylpyrazol-1-yl)borate dioxido-vanadium(V) complex [VO2{HB(3,5-Me(2)pz)(3)}] (V, pz= pyrazol-1-yl) immobilized at hierarchical MOR zeolite modified through surfactant mediated technology using NaOH as alkaline agent, V@MOR_NaOH, provides an efficient (TON up to 5.2x10(2)) catalyst for the peroxidative oxidation of cyclohexane with tert-butyl hydroperoxide to KA oil (52% yield), at room temperature, and is easily recovered and reused up to four consecutive catalytic cycles with no significant leaching of vanadium. The textural modifications performed on the zeolitic matrix produced an effective support for the anchorage of the vanadium complex allowing an improved catalytic performance and reusability. This work constitutes an unprecedented use of supported vanadium B-scorpionate complexes as catalysts for the oxidation of alkanes.
- 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.
- Fe@Hierarchical BEA zeolite catalyst for MW-assisted alcohol oxidation reaction: a greener approachPublication . Andrade, Marta A.; Ansari, Leonardo M. S.; Pombeiro, Armando; Carvalho, Ana P.; Martins, Angela; Martins, LuisaThe aim of this study was to investigate the catalytic activity of hybrid materials of iron supported on hierarchical zeolites in the oxidation reaction of 1-phenylethanol to acetophenone. A greener approach was considered for the preparation of the catalyst and performance of the oxidation reaction. Hierarchical BEA zeolite samples were obtained from an alkaline and a subsequent acid treatment. The materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen adsorption at -196 degrees C. An iron salt was incorporated onto the hierarchical zeolites by mechanochemical grinding and the catalytic performance of the prepared materials was evaluated towards the microwave assisted oxidation reaction of 1-phenylethanol. The catalyst obtained by Fe immobilization on sample modified by 0.2 M NaOH followed by acid treatment (Fe@BEA0.2AT) is the most promising material with 35% yield and 56% selectivity to acetophenone, allowing five reuse cycles without significant loss of activity and selectivity.
- 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.
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