Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerization

The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.

Influence of the Sodium/Proton replacement on the structural, morphological and photocatalytic properties of titanate nanotubes

Titanate nanotubes (TNT) with different sodium contents have been synthesised using a hydrothermal approach and a swift and highly controllable post-washing processes. The influence of the sodium/proton replacement on the structural and morphological characteristics of the prepared materials was analysed. Different optical behaviour was observed depending on the Na+/H+ samples’ content. A band gap energy of 3.27±0.03 eV was estimated for the material with higher sodium content while a value of 2.81±0.02 eV was inferred for the most protonated material, which therefore exhibits an absorption edge in the near visible region. The point of zero charge of the materials was determined and the influence of the sodium content on the adsorption of both cationic and anionic organic dyes was studied. The photocatalytic performance of the TNT samples was evaluated in the rhodamine 6G degradation process. Best photodegradation results were obtained when using the most protonated material as catalyst, although this material has shown the lowest R6G adsorption capability.

Delamination analysis of carbon fibre reinforced laminates: evaluation of a special step drill

Drilling of carbon fibre/epoxy laminates is usually carried out using standard drills. However, it is necessary to adapt the processes and/or tooling as the risk of delamination, or other damages, is high. These problems can affect mechanical properties of produced parts, therefore, lower reliability. In this paper, four different drills – three commercial and a special step (prototype) – are compared in terms of thrust force during drilling and delamination. In order to evaluate damage, enhanced radiography is applied. The resulting images were then computational processed using a previously developed image processing and analysis platform. Results show that the prototype drill had encouraging results in terms of maximum thrust force and delamination reduction. Furthermore, it is possible to state that a correct choice of drill geometry, particularly the use of a pilot hole, a conservative cutting speed – 53 m/min – and a low feed rate – 0.025 mm/rev – can help to prevent delamination.

Mode III interlaminar fracture of carbon/epoxy laminates using the edge crack torsion (ECT) test

The mode III interlaminar fracture of carbon/epoxy laminates was evaluated with the edge crack torsion (ECT) test. Three-dimensional finite element analyses were performed in order to select two specimen geometries and an experimental data reduction scheme. Test results showed considerable non-linearity before the maximum load point and a significant R-curve effect. These features prevented an accurate definition of the initiation point. Nevertheless, analyses of non-linearity zones showed two likely initiation points corresponding to GIIIc values between 850 and 1100 J/m2 for both specimen geometries. Although any of these values is realistic, the range is too broad, thus showing the limitations of the ECT test and the need for further research.

Tool geometry evaluation for carbon reinforced composite laminates

The use of composite laminates in complex structures has increased significantly. However, there are still some issues when considering their use, mainly related with machining, leading to some difficulties and lack of acceptance. In this work, a methodology to evaluate drill geometry and feed rate based on thrust force and delamination extension is presented.

Evaluation of tools and cutting conditions on carbon fibre reinforced laminates

The distinctive characteristics of carbon fibre reinforced plastics, like low weight or high specific strength, had broadened their use to new fields. Due to the need of assembly to structures, machining operations like drilling are frequent. In result of composites inhomogeneity, this operation can lead to different damages that reduce mechanical strength of the parts in the connection area. From these damages, delamination is the most severe. A proper choice of tool and cutting parameters can reduce delamination substantially. In this work the results obtained with five different tool geometries are compared. Conclusions show that the choice of an adequate drill can reduce thrust forces, thus delamination damage.

Estimation of vegetation carbon stock in Portugal using land use/ land cover data

Dissertation submitted in partial fulfilment of the requirements for the Degree of Master of Science in Geospatial Technologies

Waste recovery into activated carbon for water purification from heavy metals

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química Pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecn

alpha-Co(OH)(2)/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium

In this work, alpha-Co(OH)(2) is electrodeposited onto carbon nanofoam forming a composite electrode operating in a potential window of 2 V in aqueous medium. Prior to electrodeposition, the carbon nanofoam substrate is subjected to a functionalization process, which leads to an increase of about 40% in its specific capacitance value. Formation of cobalt hydroxide clusters onto the functionalized carbon nanofoam by pulse electrodeposition further enhances the specific capacitance of the electrode. The combination of these factors with an enlarged working potential window, results in a material with specific capacitance close to 300 F g(-1) at current density of 1 A g(-1), considering the total mass loading of the composite. This suggests the potential application of the prepared composites in high energy density electrochemical supercapacitors. (c) 2015 Elsevier B.V. All rights reserved.

MIP-graphene-modified glassy carbon electrode for the determination of trimethoprim

A novel sensitive electrochemical sensor was developed by electropolymerization of pyrrole(PY)and molecularly imprinted polymer (MIP)which was synthesized onto a glassy carbon electrode (GCE) in aqueous solution using cyclic voltammetry in the presence of Trimethoprim (TMP) as template molecules. Furthermore,a previous electrode modification was performed by deposition of a suspension of graphene on the electrode's surface. The performance of the imprinted and non-imprinted (NIP) films was evaluated by impedance spectroscopy (EIS) and cyclic voltammetry (CV) of a ferric solution. The molecularly imprinted film exhibited a high selectivity and sensitivity toward TMP. The sensor presented a linear range, between peak current intensity and logarithm of TMP concentration between 1.0x10-6 and 1.0x10-4 M. The results were accurate (with recoveries higher than 94%), precise (with standard deviations less than 5%) and the detection limit was 1.3x10-7 M. The new sensor is selective, simple to construct and easy to operate. The MIP sensor was successfully applied to quantify TMP in urinesamples.

Sensitive bi-enzymatic biosensor based on polyphenoloxidases–gold nanoparticles–chitosan hybrid film–graphene doped carbon paste electrode for carbamates detection

A bi-enzymatic biosensor (LACC–TYR–AuNPs–CS/GPE) for carbamates was prepared in a single step by electrodeposition of a hybrid film onto a graphene doped carbon paste electrode (GPE). Graphene and the gold nanoparticles (AuNPs) were morphologically characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, dynamic light scattering and laser Doppler velocimetry. The electrodeposited hybrid film was composed of laccase (LACC), tyrosinase (TYR) and AuNPs entrapped in a chitosan (CS) polymeric matrix. Experimental parameters, namely graphene redox state, AuNPs:CS ratio, enzymes concentration, pH and inhibition time were evaluated. LACC–TYR–AuNPs–CS/GPE exhibited an improved Michaelis–Menten kinetic constant (26.9 ± 0.5 M) when compared with LACC–AuNPs–CS/GPE (37.8 ± 0.2 M) and TYR–AuNPs–CS/GPE (52.3 ± 0.4 M). Using 4-aminophenol as substrate at pH 5.5, the device presented wide linear ranges, low detection limits (1.68×10− 9 ± 1.18×10− 10 – 2.15×10− 7 ± 3.41×10− 9 M), high accuracy, sensitivity (1.13×106 ± 8.11×104 – 2.19×108 ± 2.51×107 %inhibition M− 1), repeatability (1.2–5.8% RSD), reproducibility (3.2–6.5% RSD) and stability (ca. twenty days) to determine carbaryl, formetanate hydrochloride, propoxur and ziram in citrus fruits based on their inhibitory capacity on the polyphenoloxidases activity. Recoveries at two fortified levels ranged from 93.8 ± 0.3% (lemon) to 97.8 ± 0.3% (orange). Glucose, citric acid and ascorbic acid do not interfere significantly in the electroanalysis. The proposed electroanalytical procedure can be a promising tool for food safety control.

Iberian peninsula ecosystem carbon fluxes: a model-data integration study

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia do Ambiente pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia

Synthesis of biodiesel from wastes of food industry via direct transesterification with methanol/carbon dioxide mixtures

Dissertation presented at Faculdade de Ciências e Tecnologia from Universidade Nova de Lisboa to obtain the degree of Master in Chemical and Biochemical Engineering

A selecção de indicadores no estudo prospectivo “Forecasting the carbon footprint to road freight transport in 2020"

Baseado no relatório realizado para a unidade lectiva “Métodos de Análise Prospectiva” do Programa Doutoral em Avaliação de Tecnologia, 2011

RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.