Towards NIR emission: 2-(1H-tetrazol-1-yl)pyridine as versatile ligand for the synthesis of two new families of cationic and neutral Ir(III) complexes.

In the last decades, cyclometalated Ir(III) complexes have drawn a large interest for their unique properties: they are excellent triplet state emitters, thus the emission is phosphorescent in nature; typically high quantum yields and good stability make them good candidates for luminescent materials. Moreover, through an opportune choice of the ligands, it is possible to tune the emission along the whole visible spectra. Thanks to these interesting features, Ir(III) complexes have found different applications in several areas of applied science, from OLEDs to bioimaging. In particular, regarding the second application, a remarkable red-shift in the emission is required, in order to minimize the problem of the tissue penetration and the possible damages for the organisms. With the aim of synthesizing a new family of NIR emitting Ir(III) complexes, we envisaged the possibility to use for the first time 2-(1H-tetrazol-1-yl)pyridine as bidentate ligand able to provide the required red-shift of the emission of the final complexes. Exploiting the versatility of the ligand, I prepared two different families of heteroleptic Ir(III) complexes. In detail, in the first case the 2-(1H-tetrazol-1-yl)pyridine was used as bis-chelating N^N ligand, leading to cationic complexes, while in the second case it was used as cyclometalating C^N ligand, giving neutral complexes. The structures of the prepared molecules have been characterised by NMR spectroscopy and mass spectrometry. Moreover, the neutral complexes’ emissive properties have been measured: emission spectra have been recorded in solution at both room temperature and 77K, as well as in PMMA matrix. DFT calculation has then been performed and the obtained results have been compared to experimental ones.

Dynamique de l'oxygène et l'activité microbienne dans les lacs de fonte du pergélisol subarctique

Les lacs de thermokarst (lacs peu profonds créés par le dégel et l’érosion du pergélisol riche en glace) sont un type unique d’écosystèmes aquatiques reconnus comme étant de grands émetteurs de gaz à effet de serre vers l’atmosphère. Ils sont abondants dans le Québec subarctique et ils jouent un rôle important à l’échelle de la planète. Dans certaines régions, les lacs de thermokarst se transforment rapidement et deviennent plus grands et plus profonds. L’objectif de cette étude était d’améliorer la compréhension et d’évaluer quelles variables sont déterminantes pour la dynamique de l’oxygène dans ces lacs. C’est pourquoi j’ai examiné les possibles changements futurs de la dynamique de l’oxygène dans ces lacs dans un contexte de réchauffement climatique. Une grande variété de méthodes ont été utilisées afin de réaliser cette recherche, dont des analyses in situ et en laboratoire, ainsi que la modélisation. Des capteurs automatisés déployés dans cinq lacs ont mesuré l’oxygène, la conductivité et la température de la colonne d’eau en continu de l’été 2012 jusqu’à l’été 2015, à des intervalles compris entre 10 à 60 minutes. Des analyses en laboratoire ont permis de déterminer la respiration et les taux de production bactériens, les variables géochimiques limnologiques, ainsi que la distribution de la production bactérienne entre les différentes fractions de taille des communautés. La température de l’eau et les concentrations d’oxygène dissous d’un lac de thermokarst ont été modélisées avec des données du passé récent (1971) au climat futur (2095), en utilisant un scénario modéré (RCP 4.5) et un scénario plus extrême (RCP 8.5) de réchauffement climatique. Cette recherche doctorale a mis en évidence les conditions anoxiques fréquentes et persistantes présentes dans de nombreux lacs de thermokarst. Aussi, ces lacs sont stratifiés pendant l’hiver comme des concentrations élevées d’ions s’accumulent dans leurs hypolimnions à cause de la formation du couvert de glace (cryoconcentration) et de la libération des ions avec la respiration bactérienne. Les différences de température contribuent également à la stabilité de la stratification. La dynamique de mélange des lacs de thermokarst étudiés était contrastée : la colonne d’eau de certains lacs se mélangeait entièrement deux fois par année, d’autres lacs se mélangeaient qu’une seule fois en automne, alors que certains lacs ne se mélangeaient jamais entièrement. Les populations bactériennes étaient abondantes et très actives, avec des taux respiratoires comparables à ceux mesurés dans des écosystèmes méso-eutrophes ou eutrophes des zones tempérées de l’hémisphère nord. L’érosion des matériaux contenus dans le sol des tourbières pergélisolées procure un substrat riche en carbone et en éléments nutritifs aux populations bactériennes, et ils constituent des habitats propices à la colonisation par des populations de bactéries associées aux particules. Le modèle de la concentration d’oxygène dissous dans un lac a révélé que le réchauffement des températures de l’air pourrait amincir le couvert de glace et diminuer sa durée, intensifiant le transfert de l’oxygène atmosphérique vers les eaux de surface. Ainsi, la concentration en oxygène dissous dans la colonne d’eau de ce lac augmenterait et les périodes de conditions anoxiques pourraient devenir plus courtes. Finalement, cette thèse doctorale insiste sur le rôle des lacs de thermokarst comme des réacteurs biogéochimiques pour la dégradation du carbone organique, qui était retenu dans les sols gelés, en gaz à effet de serre libérés dans l’atmosphère. L’oxygène est un indicateur sensible du mélange de la colonne d’eau et de la dynamique chimique des lacs, en plus d’être une variable clé des processus métaboliques.

EXCITON ENGINEERING THROUGH TUNALBLE FLUORESCENT QUANTUM DEFECTS

This thesis demonstrates exciton engineering in semiconducting single-walled carbon nanotubes through tunable fluorescent quantum defects. By introducing different functional moieties on the sp2 lattice of carbon nanotubes, the nanotube photoluminescence is systematically tuned over 68 meV in the second near-infrared window. This new class of quantum emitters is enabled by a new chemistry that allows covalent attachment of alkyl/aryl functional groups from their iodide precursors in aqueous solution. Using aminoaryl quantum defects, we show that the pH and temperature of complex fluids can be optically measured through defect photoluminescence that encodes the local environment information. Furthermore, defect-bound trions, which are electron-hole-electron tri-carrier quasi-particles, are observed in alkylated single-walled carbon nanotubes at room temperature with surprisingly high photoluminescence brightness. Collectively, the emission from defect-bound excitons and trions in (6,5)-single walled carbon nanotubes is 18-fold brighter than that of the native exciton. These findings pave the way to chemical tailoring of the electronic and optical properties of carbon nanostructures with fluorescent quantum defects and may find applications in optoelectronics and bioimaging.

Monitoramento por microcontrolador do cultivo de spirulina em fotobiorreator raceway

A oportunidade de produção de biomassa microalgal tem despertado interesse pelos diversos destinos que a mesma pode ter, seja na produção de bioenergia, como fonte de alimento ou servindo como produto da biofixação de dióxido de carbono. Em geral, a produção em larga escala de cianobactérias e microalgas é feita com acompanhamento através de análises físicoquímicas offline. Neste contexto, o objetivo deste trabalho foi monitorar a concentração celular em fotobiorreator raceway para produção de biomassa microalgal usando técnicas de aquisição digital de dados e controle de processos, pela aquisição de dados inline de iluminância, concentração de biomassa, temperatura e pH. Para tal fim foi necessário construir sensor baseado em software capaz de determinar a concentração de biomassa microalgal a partir de medidas ópticas de intensidade de radiação monocromática espalhada e desenvolver modelo matemático para a produção da biomassa microalgal no microcontrolador, utilizando algoritmo de computação natural no ajuste do modelo. Foi projetado, construído e testado durante cultivos de Spirulina sp. LEB 18, em escala piloto outdoor, um sistema autônomo de registro de informações advindas do cultivo. Foi testado um sensor de concentração de biomassa baseado na medição da radiação passante. Em uma segunda etapa foi concebido, construído e testado um sensor óptico de concentração de biomassa de Spirulina sp. LEB 18 baseado na medição da intensidade da radiação que sofre espalhamento pela suspensão da cianobactéria, em experimento no laboratório, sob condições controladas de luminosidade, temperatura e fluxo de suspensão de biomassa. A partir das medidas de espalhamento da radiação luminosa, foi construído um sistema de inferência neurofuzzy, que serve como um sensor por software da concentração de biomassa em cultivo. Por fim, a partir das concentrações de biomassa de cultivo, ao longo do tempo, foi prospectado o uso da plataforma Arduino na modelagem empírica da cinética de crescimento, usando a Equação de Verhulst. As medidas realizadas no sensor óptico baseado na medida da intensidade da radiação monocromática passante através da suspensão, usado em condições outdoor, apresentaram baixa correlação entre a concentração de biomassa e a radiação, mesmo para concentrações abaixo de 0,6 g/L. Quando da investigação do espalhamento óptico pela suspensão do cultivo, para os ângulos de 45º e 90º a radiação monocromática em 530 nm apresentou um comportamento linear crescente com a concentração, apresentando coeficiente de determinação, nos dois casos, 0,95. Foi possível construir um sensor de concentração de biomassa baseado em software, usando as informações combinadas de intensidade de radiação espalhada nos ângulos de 45º e 135º com coeficiente de determinação de 0,99. É factível realizar simultaneamente a determinação inline de variáveis do processo de cultivo de Spirulina e a modelagem cinética empírica do crescimento do micro-organismo através da equação de Verhulst, em microcontrolador Arduino.

Faint Galaxies in the Megaparsec-Scale Environments of Hyperluminous QSOs at Redshifts 2 < z < 3

This thesis presents detailed observational studies of the extended distributions of gas, galaxies, and dark matter around hyperluminous quasars (HLQSOs) at high redshift. Taken together, these works aim to coherently describe the relationships between these massive, accreting black holes and their environments: the nature of the regions that give rise to such massive black holes, the effect of HLQSO radiation on their surrounding galaxies and gas, and the ability of both galaxies and black holes to shed new light on the formation and evolution of the other.

Chapter 2 focuses on the continuum-color-selected galaxies drawn from the Keck Baryonic Structure Survey (KBSS). The KBSS is a uniquely deep spectroscopic survey of star-forming galaxies in the same volumes of space as 15 HLQSOs at 2.5 < z < 2.9. The three-dimensional distribution of these galaxies among themselves and the nearby HLQSOs is used to infer the extent to which these black holes are associated with overdense peaks in the dark matter and galaxy distribution as quantified by clustering statistics. In conjunction with recent dark-matter simulations, these data provide the first estimates of the host dark-matter halo masses for HLQSOs, providing new insight into the formation and evolution of the most massive black holes at high redshift.

Chapter 3 describes the first results from a new survey (KBSS-Lyα) conducted for this thesis. The KBSS-Lyα survey uses narrowband imaging to identify Lyα-emitters (LAEs) in the ~Mpc regions around eight of the KBSS HLQSOs. Many of these LAEs show the effect of reprocessed HLQSO radiation in their emission through the process known as Lyα fluorescence. In this chapter, these fluorescent LAEs are used to generate a coarse map of the average HLQSO ionizing emission on Mpc scales, thereby setting the first direct constraints of the lifetime and angular distribution of activity for a population of these uniquely luminous black holes.

Chapter 4 contains a more detailed description of the KBSS-Lyα survey itself and the detailed properties of the star-forming and fluorescent objects selected therein. Using imaging and spectroscopic data covering rest-frame UV and optical wavelengths, including spectra from the new near-infrared spectrometer MOSFIRE, we characterize this population of nascent galaxies in terms of their kinematics, enrichment, gas properties, and luminosity distribution while comparing and contrasting them with previously-studied populations of continuum-selected galaxies and LAEs far from the effects of HLQSO emission.

At the conclusion of this thesis, I briefly present future directions for the continuation of this research. In Appendix A, I provide background information on the instrumentation used in this thesis, including my own contributions to MOSFIRE.

Graphene and Semicondutor or Metallic Nanoparticles for Energy Conversion

The purpose of the present PhD thesis is to investigate the properties of innovative nano- materials with respect to the conversion of renewable energies to electrical and chemical energy. The materials have been synthesized and characterized by means of a wide spectrum of morphological, compositional and photophysical techniques, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. Two main topics are addressed: in the first part of the thesis the light harvesting in pyrene functionalized silicon nanocrystals has been discussed, suggesting an original approach to suc- cessfully increase the absorption properties of these nanocrystals. The interaction of these nanocrystals was then studied, in order to give a deeper insight on the charge and energy extraction, preparing the way to implement SiNCs as active material in optoelectronic devices and photovoltaic cells. In addition to this, the luminescence of SiNCs has been exploited to increase the efficiency of conventional photovoltaic cells by means of two innovative architectures. Specifically, SiNCs has been used as luminescent downshifting layer in dye sensitized solar cells, and they were shown to be very promising light emitters in luminescent solar concentrators. The second part of the thesis was concerned on the production of hydrogen by platinum nanoparticles coupled to either electro-active or photo-active materials. Within this context, the electrocatalytic activity of platinum nanoparticles supported on exfoliated graphene has been studied, preparing an high-efficiency catalyst and disclosing the role of the exfoliation technique towards the catalytic activity. Furthermore, platinum nanoparticles have been synthesized within photoactive dendrimers, providing the first proof of concept of a dendrimer-based photocatalytic system for the hydrogen production where both sensitizer and catalyst are anchored to a single scaffold.

Plugged ducts

This sheet printed in both English and Spanish discusses plugged or clogged ducts during breastfeeding, their prevention and treatment.

Superior color rendering with a phosphor-converted blue-cyan monolithic light-emitting diode

The future generation of modern illumination should not only be cheap and highly efficient, but also demonstrate high quality of light, light which allows better color differentiation and fidelity. Here we are presenting a novel approach to create a white solid-state light source providing ultimate color rendition necessary for a number of applications. The proposed semi-hybrid device combines a monolithic blue-cyan light emitting diode (MBC LED) with a green-red phosphor mixture. It has shown a superior color rendering index (CRI), 98.6, at correlated color temperature of around 3400 K. The MBC LED epi-structure did not suffer from the efficiency reduction typical for monolithic multi-color emitters and was implemented in the two most popular chip designs: “epi-up” and “flip-chip”. Redistribution of the blue and cyan band amplitudes in the white-light emission spectrum, using the operating current, is found to be an effective tool for fine tuning the color characteristics. (Figure presented.).

Roteiro Tecnológico (roadmap) da Captação, Utilização e Armazenamento de Dióxido de Carbono (CCUS) em Portugal

O objetivo primordial deste trabalho foi estabelecer um roteiro tecnológico para aplicação das tecnologias de “Captação, Utilização e Sequestração de Carbono - CCUS” em Portugal. Para o efeito procedeu-se à identificação da origem das maiores fontes emissoras estacionárias industriais de CO2, adotando como critério o valor mínimo de 1×105 ton CO2/ano e limitado apenas ao território continental. Com base na informação recolhida e referente aos dados oficiais mais recentes (ano de 2013), estimou-se que o volume de emissões industriais de CO2 possível de captar em Portugal, corresponde a cerca de 47 % do valor global das emissões industriais, sendo oriundo de três setores de atividade industrial: produção de cimento, de pasta de papel e centrais termoelétricas a carvão. A maioria das grandes fontes emissoras industriais localiza-se no litoral do país, concentrando-se entre Aveiro e Sines. Pelas condicionantes geográficas do país e, sobretudo pela vantagem de já existir uma rede de gasodutos para o transporte de gás natural, com as respetivas infraestruturas de apoio associadas, admitiu-se que o cenário mais favorável para o transporte do CO2 captado será a criação de um sistema de transporte por gasoduto específico para o CO2. Como critério de compatibilização da proximidade das fontes emissoras de CO2 com potenciais locais para o armazenamento geológico das correntes captadas, adotou-se a distância máxima de 100 km, considerada adequada perante a dimensão do território nacional e as características do tecido industrial nacional. Efetuou-se a revisão das tecnologias de captação de CO2 disponíveis, quer comercialmente, quer em níveis avançados de demonstração e procedeu-se à análise exploratória da adequação desses diferentes métodos de captação a cada um dos setores de atividade industrial previamente identificados com emissões de CO2 suscetíveis de serem captadas. Na perspetiva da melhor integração dos processos, esta análise preliminar tomou em consideração as características das misturas gasosas, assim como o contexto industrial correspondente e o processo produtivo que lhe dá origem. As possibilidades de utilização industrial do CO2 sujeito à captação no país foram tratadas neste trabalho de forma genérica dado que a identificação de oportunidades reais para a utilização de correntes de CO2 captadas exige uma análise de compatibilização das necessidades efetivas de utilização de CO2 por parte de potenciais utilizadores industriais que carece da caracterização prévia das propriedades dessas correntes. Este é um tipo de análise muito específico que pressupõe o interesse mútuo de diferentes intervenientes: agentes emissores de CO2, operadores de transporte e, principalmente, potenciais utilizadores de CO2 como: matéria-prima para a síntese de compostos, solvente de extração supercrítica na indústria alimentar ou farmacêutica, agente corretor de pH em tratamento de efluentes, biofixação por fotossíntese, ou outra das aplicações possíveis identificadas para o CO2 captado. A última etapa deste estudo consistiu na avaliação das possibilidades de armazenamento geológico do CO2 captado e envolveu a identificação, nas bacias sedimentares nacionais, de formações geológicas com características reconhecidas como sendo boas indicações para o armazenamento de CO2 de forma permanente e em segurança. Seguiu-se a metodologia preconizada por organizações internacionais aplicando à situação nacional, critérios de seleção e de segurança que se encontram reconhecidamente definidos. A adequação para o armazenamento de CO2 das formações geológicas pré-selecionadas terá que ser comprovada por estudos adicionais que complementem os dados já existentes sobre as características geológicas destas formações e, mais importante ainda, por testes laboratoriais e ensaios de injeção de CO2 que possam fornecer informação concreta para estimar a capacidade de sequestração e de retenção de CO2 nestas formações e estabelecer os modelos geológicos armazenamento que permitam identificar e estimar, de forma concreta e objetiva, os riscos associados à injeção e armazenamento de CO2.

Síndrome da boca ardente

Resumo: O presente trabalho trata-se de uma revisão da literatura existente acerca da Síndrome da Boca Ardente e é colmatado com a apresentação de um caso clínico. Nele são apresentados e discutidos todos os parâmetros da doença com o objectivo final de apresentar e confrontar a informação já existente. O trabalho foi elaborado sempre visando a aplicação da informação na prática clínica do médico dentista generalista. Introdução: A Síndrome da Boca Ardente é uma doença identificada pela International Association for the Study of Pain como “uma entidade nosológica distinta” caracterizada por “sensação de dor ou ardor incessante acompanhada pela ausência de alterações objectivas na mucosa oral”. Objectivo: Apresentar as características da doença e organizar a informação com o intuito da sua aplicação prática. Materiais e métodos: Foi realizada uma pesquisa em duas bases de dados Pubmed e Scielo. Foram utilizados apenas artigos em inglês e preferivelmente com data de publicação a partir de 2000, embora não tenham sido usados limites temporais. O critério de inclusão foi o acesso ao texto integral. Conclusão: Foi possível concluir que é ainda necessário aprofundar a investigação no que diz respeito à fisiopatologia da doença, para que se avance para conclusões acerca da manutenção e tratamento de um paciente com Síndrome da Boca Ardente. Por outro lado, depois da organização das evidências relativas à história médica e exame clínico, a questão que se prende com o atraso de diagnóstico é uma que é merece atenção e para a qual a transmissão de informação parece ser a solução.

Nitrate and potassium concentration in fertigated soil cultivated with wine vines.

In the semiarid region of Brazil the use of irrigation systems for applying fertilizers in horticulture is the primary means for incorporating nutrients in the soil. However, this technique still requires its use in wine vines to be assessed. In view of this, this study aimed to assess nitrate and potassium concentrations in soil fertigated with nitrogen and potassium fertilizers in 3 wine grape growing cycles. A field experiment was conducted with ?Syrah? wine grapes, in Petrolina, Pernambuco, Brazil; it assessed five nitrogen doses (0, 15, 30, 60 and 120 kg ha-1) and five K2O doses (0, 15, 30, 60 and 120 kg ha-1) applied by drip irrigation system with two emitters per plant, with a flow rate of 4 L h-1. The experimental design used was the factorial split-plot, making up 13 combinations arranged in 4 randomized blocks. Soil solution samples were collected weekly with the aid of porous cup extractors for all treatments and at depths of 0.4 and 0.6 m by determining nitrate and potassium concentrations and electrical conductivity. Increased levels of both nutrients in the irrigation water increased the availability of nitrate and potassium in the soil solution. The highest nitrate and potassium concentrations were found in the second growing cycle at both depths studied.

Dynamic Modeling and Seasonal Performance Evaluation of Air-to-Water Heat Pump Systems

In this Thesis a series of numerical models for the evaluation of the seasonal performance of reversible air-to-water heat pump systems coupled to residential and non-residential buildings are presented. The exploitation of the energy saving potential linked to the adoption of heat pumps is a hard task for designers due to the influence on their energy performance of several factors, like the external climate variability, the heat pump modulation capacity, the system control strategy and the hydronic loop configuration. The aim of this work is to study in detail all these aspects. In the first part of this Thesis a series of models which use a temperature class approach for the prediction of the seasonal performance of reversible air source heat pumps are shown. An innovative methodology for the calculation of the seasonal performance of an air-to-water heat pump has been proposed as an extension of the procedure reported by the European standard EN 14825. This methodology can be applied not only to air-to-water single-stage heat pumps (On-off HPs) but also to multi-stage (MSHPs) and inverter-driven units (IDHPs). In the second part, dynamic simulation has been used with the aim to optimize the control systems of the heat pump and of the HVAC plant. A series of dynamic models, developed by means of TRNSYS, are presented to study the behavior of On-off HPs, MSHPs and IDHPs. The main goal of these dynamic simulations is to show the influence of the heat pump control strategies and of the lay-out of the hydronic loop used to couple the heat pump to the emitters on the seasonal performance of the system. A particular focus is given to the modeling of the energy losses linked to on-off cycling.

Computational characterization of carbazole-benzonitrile derivatives for applications in Organic Light Emitting Diodes

The technology of Organic Light-Emitting Diodes has reached such a high level of reliability that it can be used in various applications. The required light emission efficiency can be achieved by transforming the triplet excitons into singlet states through Reverse InterSystem Crossing (RISC), which is the main process of a general mechanism called thermally activated delayed fluorescence (TADF). In this thesis, we theoretically analyzed two carbazole-benzonitrile (donor-acceptor) derivatives, 2,5-di(9H-carbazol-9-yl)benzonitrile (p-2CzBN) and 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN), and addressed the problem of how donor-acceptor (D-A) or donor-acceptor-donor (D-A-D) flexible molecular architectures influence the nature of the excited states and the emission intensity. Furthermore, we analyzed the RISC rates as a function of the conformation of the carbazole lateral groups, considering the first electronic states, S0, S1, T1 and T2, involved in TADF process. The two prototype molecules, p-2CzBN and 5CzBN, have a similar energy gap between the first singlet and triplet states (∆EST, a key parameter in the RISC rate), but different TADF performances. Therefore, other parameters must be considered to explain their different behavior. The oscillator strength of p-2CzBN, never tested as emitter in OLEDs, is similar to that of 5CzBN, which is an active TADF molecule. We also note that the presence of a second T2 triplet state, lower in energy than S1 only in 5CzBN, and the reorganization energies, associated with RISC processes involving T1 and T2, are important factors in differentiating the rates in p-2CzBN and 5CzBN. For p-2CzBN, the RISC rate from T2 to S1 is surprisingly higher than that from T1 to S1, in disagreement with El-Sayed rules, due to a large reorganization energy associated to the T1 to S1, process; while the contrary occurs for 5CzBN. These insights are important for designing new TADF emitters based on the benzo-carbazole architecture.

Light & Electron beam - the perfect combination for the observation and application of photo active materials

The aim of the present PhD thesis is to investigate the properties of innovative nanomaterials for energy conversion. The materials have been deeply studied by means of a wide spectrum of different techniques based on both light and electron sources, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. The activity has been carried out in the framework of a collaboration between the “G.Ciamician” Chemistry Department of the University of Bologna and the CNR-IMM Bologna. Four main topics have been explored: in the first part, luminescent silicon nanocrystals (SiNCs) have been discussed, suggesting a new approach to improve their optical properties as active material in complementary optoelectronic devices and photovoltaic cells. The luminescence of SiNCs have been exploited to increase the efficiency of conventional photovoltaic cells by means of an innovative architecture. Specifically, SiNCs were shown to be very promising light emitters in luminescent solar concentrators (LSC). The second part of the work has been focused on the study of high phosphorescent molecular chromophores, suggesting a new approach in their use as optical sensors successfully applied to the field of polymeric materials. This is due to the enhanced emission of light that appears in rigid, constrained or crystalline state, that is commonly called: "Aggregation-Induced Emission (AIE)". Such phenomenon is characteristic for molecular structures such as persulfurated benzene chromophores, hereafter named asterisks. The last two parts were focused on conventional and in-situ Transmission Electron Microscopy (TEM) morphological and structural characterization of photoactive and catalytic materials for energetic applications and in particular water splitting.

Chemical looping reforming from methane to syngas: investigation on CeO2 oxygen carrier lifetime and optimal process times

Emissions of CO2 are constantly growing since the beginning of industrial era. Interruption of the production of major emitters sectors (energy and agriculture) is not a viable way and reducing all the emission through carbon capture and storage (CCS) is not economically viable and little publicly accepted, therefore, it becomes fundamentals to take actions like retrofitting already developed infrastructure employing cleanest resources, modify the actual processes limiting the emissions, and reduce the emissions already present through direct air capture. The present thesis will deeply discuss the aspects mentioned in regard to syngas and hydrogen production since they have a central role in the market of energy and chemicals. Among the strategies discussed, greater emphasis is given to the application of looping technologies and to direct air capture processes, as they have been the main point of this work. Particularly, chemical looping methane reforming to syngas was studied with Aspen Plus thermodynamic simulations, thermogravimetric analysis characterization (TGA) and testing in a fixed bed reactor. The process was studied cyclically exploiting the redox properties of a Ce-based oxide oxygen carrier synthetized with a simple forming procedure. The two steps of the looping cycles were studied isothermally at 900 °C and 950° C with a mixture of 10 %CH4 in N2 and of 3% O2 in N2, for carrier reduction and oxidation, respectively. During the stay abroad, in collaboration with the EHT of Zurich, a CO2 capture process in presence of amine solid sorbents was investigated, studying the difference in the performance achievable with the use of contactors of different geometry. The process was studied at two concentrations (382 ppm CO2 in N2 and 5.62% CO2 in N2) and at different flow rates, to understand the dynamics of the adsorption process and to define the mass transfer limiting step.