Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite

The hydrotris(pyrazol-1-yl)methane iron(II) complex [FeCl2{eta(3)-HC(pz)(3)}] (Fe, pz = pyrazol-1-yl) immobilized on commercial (MOR) or desilicated (MOR-D) zeolite, catalyses the oxidation of cyclohexane with hydrogen peroxide to cyclohexanol and cyclohexanone, under mild conditions. MOR-D/Fe (desilicated zeolite supported [FeCl2{eta(3)-HC(pz)(3)}] complex) provides an outstanding catalytic activity (TON up to 2.90 x 10(3)) with the concomitant overall yield of 38%, and can be easy recovered and reused. The MOR or MOR-D supported hydrotris(pyrazol-1-yl)methane iron(II) complex (MOR/Fe and MOR-D/Fe, respectively) was characterized by X-ray powder diffraction, ICP-AES, and TEM studies as well as by IR spectroscopy and N-2 adsorption at -196 degrees C. The catalytic operational conditions (e.g., reaction time, type and amount of oxidant, presence of acid and type of solvent) were optimized. (C) 2013 Elsevier B.V. All rights reserved.

Síntese e caracterização de redes metalo-orgânicas de fármacos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

Projecto timecloud: software de gestão de tempo laboral numa plataforma cloud

O presente projecto tem como objectivo a disponibilização de uma plataforma de serviços para gestão e contabilização de tempo remunerável, através da marcação de horas de trabalho, férias e faltas (com ou sem justificação). Pretende-se a disponibilização de relatórios com base nesta informação e a possibilidade de análise automática dos dados, como por exemplo excesso de faltas e férias sobrepostas de trabalhadores. A ênfase do projecto está na disponibilização de uma arquitectura que facilite a inclusão destas funcionalidades. O projecto está implementado sobre a plataforma Google App Engine (i.e. GAE), de forma a disponibilizar uma solução sob o paradigma de Software as a Service, com garantia de disponibilidade e replicação de dados. A plataforma foi escolhida a partir da análise das principais plataformas cloud existentes: Google App Engine, Windows Azure e Amazon Web Services. Foram analisadas as características de cada plataforma, nomeadamente os modelos de programação, os modelos de dados disponibilizados, os serviços existentes e respectivos custos. A escolha da plataforma foi realizada com base nas suas características à data de iniciação do presente projecto. A solução está estruturada em camadas, com as seguintes componentes: interface da plataforma, lógica de negócio e lógica de acesso a dados. A interface disponibilizada está concebida com observação dos princípios arquitecturais REST, suportando dados nos formatos JSON e XML. A esta arquitectura base foi acrescentada uma componente de autorização, suportada em Spring-Security, sendo a autenticação delegada para os serviços Google Acounts. De forma a permitir o desacoplamento entre as várias camadas foi utilizado o padrão Dependency Injection. A utilização deste padrão reduz a dependência das tecnologias utilizadas nas diversas camadas. Foi implementado um protótipo, para a demonstração do trabalho realizado, que permite interagir com as funcionalidades do serviço implementadas, via pedidos AJAX. Neste protótipo tirou-se partido de várias bibliotecas javascript e padrões que simplificaram a sua realização, tal como o model-view-viewmodel através de data binding. Para dar suporte ao desenvolvimento do projecto foi adoptada uma abordagem de desenvolvimento ágil, baseada em Scrum, de forma a implementar os requisitos do sistema, expressos em user stories. De forma a garantir a qualidade da implementação do serviço foram realizados testes unitários, sendo também feita previamente a análise da funcionalidade e posteriormente produzida a documentação recorrendo a diagramas UML.

Desilication of MOR zeolite: Conventional versus microwave assisted heating

MOR zeolites were modified via desilication treatments with NaOH, under conventional and microwave heating. The samples were characterized by powder X-ray diffraction, (27)Al and (29)Si NMR spectroscopy. TEM and N(2) adsorption at -196 degrees C. The acidity of the samples and the space available inside the pores were evaluated through a catalytic model reaction, the isomerization of m-xylene, for which the profiles of the coke thermal decomposition were also analyzed. Powder X-ray diffraction and (29)Si and (27)Al MNR results show that in comparison with conventional heating, microwave irradiation (a less time consuming process) leads to identical amount of Si extraction from the zeolite framework. With this treatment. in addition to the customary mesopores development promoted by conventional heating, a partial conversion of the zeolite microporosity into larger micropores, is observed. The microwave irradiated and conventionally heated samples show different catalytic behavior in the m-xylene isomerization model reaction. It was observed that, by controlling the experimental conditions, it is possible to obtain samples with catalytic properties closer to the parent material, which is also confirmed by the respective coke analysis. (C) 2011 Elsevier B.V. All rights reserved.

Relatório de projeto Milk Run Software

Em suma este trabalho de projeto visa a criação de uma ferramenta que permita a gestão dos transportes para a recolha de matéria-prima necessária ao bom funcionamento da fábrica de produção automóvel Volkswagen Autoeuropa num ambiente dinâmico, sendo esta desenvolvida para responder às necessidades da empresa. Assim foi desenvolvido o protótipo Milk Run Software que consiste basicamente na integração de informação fornecida pela empresa relativa a consumos de materiais provenientes de ordens de produção, fornecedores e transportes. Com base nestes dados e recurso a sistemas externos é efetuada a georreferenciação de fornecedores para que exista a noção de proximidade entre estes, além disso foi construído um sistema de decisão, para que com base nos consumos (peças, pesos e volumes), se consigam determinar e gerir as rotas de transportes da empresa Volkswagen Autoeuropa com base no conceito Milk Run, que consiste na otimização do transporte de peças para montagem de veículos, no qual tem em conta a localização geográfica, o volume ou peso a transportar, as limitações físicas dos veículos de transporte, bem como o número de paragens máximas (cargas a efetuar no percurso). Neste projeto são utilizadas diversas técnicas de análise protagonizadas para a construção de ferramentas com o recurso à Engenharia de Software, e a algumas técnicas na área de pesquisa em espaços de estado para auxiliar o conceito Milk Run para resolução dos problemas encontrados.

Estudo da percepção dos problemas de usabilidade de um software relacionados com o desempenho dos processos cognitivos

Dissertação apresentada à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Audiovisual e Multimédia.

Simulação, em software adequado, da sintomatologia vibracional de avarias mecânicas de máquinas rotativas

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica na Área de Manutenção e Produção

Buying behavior and competition in the software market

In the actual world, the impact of the software buying decisions has a rising relevance in social and economic terms. This research tries to explain it focusing on the organizations buying decisions of Operating Systems and Office Suites for personal computers and the impact on the competition between incumbent and alternative players in the market in these software categories, although the research hypotheses and conclusions may extend to other software categories and platforms. We concluded that in this market beside brand image, product features or price, other factors could have influence in the buying choices. Network effect, switching costs, local network effect, lock-in or consumer heterogeneity all have influence in the buying decision, protecting the incumbent and making it difficult for the competitive alternatives, based mainly on product features and price, to gain market share to the incumbent. This happens in a stronger way in the Operating Systems category.

Influencing factors on the buying behavior in the software market

The case of desktop Operating System and Office Suite choices considering Proprietary and Open Source Software alternatives.

Catalytic behavior of alkali-treated Pt/HMOR n-hexane hydroisomerization

Bifunctional Pt-HMOR catalysts were prepared by incipient wetness impregnation of various desilicated MOR obtained by alkaline treatment using NaOH concentrations ranging from 0.1 to 0.5 M. The zeolite structural changes upon modification were investigated by several techniques including powder X-ray diffraction,Al-27 and Si-29 MAS-NMR spectroscopy, N-2 adsorption, pyridine adsorption followed by infrared spectroscopy and the catalytic model reaction of m-xylene transformation. For low alkaline concentration the zeolite acidity is preserved, along with a slight increase of the volume correspondent to the larger micropores due to the removal of extra-framework debris already existent at the parent zeolite. At higher NaOH concentrations there is a significant loss of crystalinity and acidity as well as the formation of mesoporosity. The characterization of the metal function shows similar patterns for Pt-HMOR and Pt-M/0.1 samples, with Pt particles located mainly inside the inner porosity. In contrast, large Pt particles become visible at the intercrystalline mesoporosity of MOR crystals developed during the desilication treatments at severe alkaline conditions. The catalytic results obtained for n-hexane hydroisomerization showed an improved selectivity for dibranched over monobranched isomers for Pt-M/0.1 sample, likely due to the preservation of the support acidity and the slight enlargement of the micropores. This work is a new example in which the mesoporous development does not improve the catalytic efficiency of the zeolites, whereas mild alkaline desilication might be considered as an effective solution to produce customized catalysts with enhanced performance for a given application. (C) 2014 Elsevier B.V. All rights reserved.

Modifications of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour

Desilication and a combination of alkaline followed by acid treatment were applied to MCM-22 zeolite using two different base concentrations. The samples were characterised by powder X-ray diffraction, Al-27 and Si-29 MAS-NMR spectroscopy, SEM, TEM and low temperature N-2 adsorption. The acidity of the samples was study through pyridine adsorption followed by FTIR spectroscopy and by the analyses of the hydroxyl region. The catalytic behaviour, anticipated by the effect of post-synthesis treatments on the acidity and space available inside the two internal pore systems was evaluated by using the model reaction of m-xylene transformation. The generation of mesoporosity was achieved upon alkaline treatment with 0.05 M NaOH solution and practically no additional gain was obtained when the more concentrate solution, 0.1 M, was used. Instead, Al extraction takes place along with Si, as shown by Si-29 and Al-27 MAS-NMR data, followed by Al deposition as extraframework species. Samples submitted to alkaline plus acid treatments present distinct behaviour. When the lowest NaOH solution was used no relevant effect was observed on the textural characteristics. Additionally, when the acid treatment was performed on an already fragilized MCM-22 structure, due to previous desilication with 0.1 M NaOH solution, the extraction of Al from both internal pore systems promotes their interconnection, evolving from a 2-D to a 3-D porous structure. This transformation has a marked effect in the catalytic behaviour, allowing an increase of m-xylene conversion as a consequence of an easier and faster molecular traffic in the 3-D structure. On the other hand, the continuous deposition of extraframework Al species inside the pores leads to a shape selective effect that privileges the formation of the more valuable isomer p-xylene.

Contributos didático-pedagógicos do software smartmusic no ensino do clarinete

Mestrado em Ensino da Música.

Toroid inductor development for a SIC DC-DC converter up to 150kW, based on finite element method

Dissertação para a obtenção do grau de Mestre em Engenharia Electrotécnica Ramo de Energia