Photophysical investigation of light-harvesting systems for solar-to-fuel conversion

In recent years, an increasing attention has been given to the optimization of the performances of new supramolecular systems, as antennas for light collection. In such background, the aim of this thesis was the study of multichromophoric architectures capable of performing such basic action. A synthetic antenna should consist of a structure with large UV-Vis absorption cross-section, panchromatic absorption, fixed orientation of the components and suitable energy gradients between them, in order to funnel absorbed energy towards a specific site, through fast energy-transfer processes. Among the systems investigated in this thesis, three suitable classes of compounds can be identified: 1) transition metal-based multichromophoric arrays, as models for antenna construction, 2) free-base trans-A2B-phenylcorroles, as self-assembling systems to make effective mimics of the photosynthetic system, and 3) a natural harvester, the Photosystem I, immobilized on the photoanode of a solar-to-fuel conversion device. The discussion starts with the description of the photophysical properties of dinuclear quinonoid organometallic systems, able to fulfil some of the above mentioned absorption requirements, displaying in some cases panchromatic absorption. The investigation is extended to the efficient energy transfer processes occurring in supramolecular architectures, suitably organized around rigid organic scaffolds, such as spiro-bifluorene and triptycene. Furthermore, the photophysical characterization of three trans-A2B-phenylcorroles with different substituents on the meso-phenyl ring is introduced, revealing the tendency of such macrocycles to self-organize into dimers, by mimicking natural self-aggregates antenna systems. In the end, the photophysical analysis moved towards the natural super-complex PSI-LHCI, immobilized on the hematite surface of the photoanode of a bio-hybrid dye-sensitized solar cell. The importance of the entire work is related to the need for a deep understanding of the energy transfer mechanisms occurring in supramolecules, to gain insights and improve the strategies for governing the directionality of the energy flow in the construction of well-performing antenna systems.

Dynamic power management: from portable devices to high performance computing

Electronic applications are nowadays converging under the umbrella of the cloud computing vision. The future ecosystem of information and communication technology is going to integrate clouds of portable clients and embedded devices exchanging information, through the internet layer, with processing clusters of servers, data-centers and high performance computing systems. Even thus the whole society is waiting to embrace this revolution, there is a backside of the story. Portable devices require battery to work far from the power plugs and their storage capacity does not scale as the increasing power requirement does. At the other end processing clusters, such as data-centers and server farms, are build upon the integration of thousands multiprocessors. For each of them during the last decade the technology scaling has produced a dramatic increase in power density with significant spatial and temporal variability. This leads to power and temperature hot-spots, which may cause non-uniform ageing and accelerated chip failure. Nonetheless all the heat removed from the silicon translates in high cooling costs. Moreover trend in ICT carbon footprint shows that run-time power consumption of the all spectrum of devices accounts for a significant slice of entire world carbon emissions. This thesis work embrace the full ICT ecosystem and dynamic power consumption concerns by describing a set of new and promising system levels resource management techniques to reduce the power consumption and related issues for two corner cases: Mobile Devices and High Performance Computing.

Numerical optimization,modeling and system evaluation of a thermophotovoltaic hybrid panel

Photovoltaic (PV) solar panels generally produce electricity in the 6% to 16% efficiency range, the rest being dissipated in thermal losses. To recover this amount, hybrid photovoltaic thermal systems (PVT) have been devised. These are devices that simultaneously convert solar energy into electricity and heat. It is thus interesting to study the PVT system globally from different point of views in order to evaluate advantages and disadvantages of this technology and its possible uses. In particular in Chapter II, the development of the PVT absorber numerical optimization by a genetic algorithm has been carried out analyzing different internal channel profiles in order to find a right compromise between performance and technical and economical feasibility. Therefore in Chapter III ,thanks to a mobile structure built into the university lab, it has been compared experimentally electrical and thermal output power from PVT panels with separated photovoltaic and solar thermal productions. Collecting a lot of experimental data based on different seasonal conditions (ambient temperature,irradiation, wind...),the aim of this mobile structure has been to evaluate average both thermal and electrical increasing and decreasing efficiency values obtained respect to separate productions through the year. In Chapter IV , new PVT and solar thermal equation based models in steady state conditions have been developed by software Dymola that uses Modelica language. This permits ,in a simplified way respect to previous system modelling softwares, to model and evaluate different concepts about PVT panel regarding its structure before prototyping and measuring it. Chapter V concerns instead the definition of PVT boundary conditions into a HVAC system . This was made trough year simulations by software Polysun in order to finally assess the best solar assisted integrated structure thanks to F_save(solar saving energy)factor. Finally, Chapter VI presents the conclusion and the perspectives of this PhD work.

Interference Management and Energy Efficiency in Satellite Communications

The main areas of research of this thesis are Interference Management and Link-Level Power Efficiency for Satellite Communications. The thesis is divided in two parts. Part I tackles the problem of interference environments in satellite communications, and interference mitigation strategies, not just in terms of avoidance of the interferers, but also in terms of actually exploiting the interference present in the system as a useful signal. The analysis follows a top-down approach across different levels of investigation, starting from system level consideration on interference management, down to link-level aspects and to intra-receiver design. Interference Management techniques are proposed at all the levels of investigation, with interesting results. Part II is related to efficiency in the power domain, for instance in terms of required Input Back-off at the power amplifiers, which can be an issue for waveform based on linear modulations, due to their varying envelope. To cope with such aspects, an analysis is carried out to compare linear modulation with waveforms based on constant envelope modulations. It is shown that in some scenarios, constant envelope waveforms, even if at lower spectral efficiency, outperform linear modulation waveform in terms of energy efficiency.

Copper(I) phenanthroline complexes and supramolecular systems containing fullerenes: Photophysics, photochemistry and potential applications in sustainable energy technologies.

Chemistry can contribute, in many different ways to solve the challenges we are facing to modify our inefficient and fossil-fuel based energy system. The present work was motivated by the search for efficient photoactive materials to be employed in the context of the energy problem: materials to be utilized in energy efficient devices and in the production of renewable electricity and fuels. We presented a new class of copper complexes, that could find application in lighting techhnologies, by serving as luminescent materials in LEC, OLED, WOLED devices. These technologies may provide substantial energy savings in the lighting sector. Moreover, recently, copper complexes have been used as light harvesting compounds in dye sensitized photoelectrochemical solar cells, which offer a viable alternative to silicon-based photovoltaic technologies. We presented also a few supramolecular systems containing fullerene, e.g. dendrimers, dyads and triads.The most complex among these arrays, which contain porphyrin moieties, are presented in the final chapter. They undergo photoinduced energy- and electron transfer processes also with long-lived charge separated states, i.e. the fundamental processes to power artificial photosynthetic systems.

Design methodologies of microwawe integrated circuits for satellite telecommunications

The running innovation processes of the microwave transistor technologies, used in the implementation of microwave circuits, have to be supported by the study and development of proper design methodologies which, depending on the applications, will fully exploit the technology potentialities. After the choice of the technology to be used in the particular application, the circuit designer has few degrees of freedom when carrying out his design; in the most cases, due to the technological constrains, all the foundries develop and provide customized processes optimized for a specific performance such as power, low-noise, linearity, broadband etc. For these reasons circuit design is always a “compromise”, an investigation for the best solution to reach a trade off between the desired performances. This approach becomes crucial in the design of microwave systems to be used in satellite applications; the tight space constraints impose to reach the best performances under proper electrical and thermal de-rated conditions, respect to the maximum ratings provided by the used technology, in order to ensure adequate levels of reliability. In particular this work is about one of the most critical components in the front-end of a satellite antenna, the High Power Amplifier (HPA). The HPA is the main power dissipation source and so the element which mostly engrave on space, weight and cost of telecommunication apparatus; it is clear from the above reasons that design strategies addressing optimization of power density, efficiency and reliability are of major concern. Many transactions and publications demonstrate different methods for the design of power amplifiers, highlighting the availability to obtain very good levels of output power, efficiency and gain. Starting from existing knowledge, the target of the research activities summarized in this dissertation was to develop a design methodology capable optimize power amplifier performances complying all the constraints imposed by the space applications, tacking into account the thermal behaviour in the same manner of the power and the efficiency. After a reminder of the existing theories about the power amplifier design, in the first section of this work, the effectiveness of the methodology based on the accurate control of the dynamic Load Line and her shaping will be described, explaining all steps in the design of two different kinds of high power amplifiers. Considering the trade-off between the main performances and reliability issues as the target of the design activity, we will demonstrate that the expected results could be obtained working on the characteristics of the Load Line at the intrinsic terminals of the selected active device. The methodology proposed in this first part is based on the assumption that designer has the availability of an accurate electrical model of the device; the variety of publications about this argument demonstrates that it is so difficult to carry out a CAD model capable to taking into account all the non-ideal phenomena which occur when the amplifier operates at such high frequency and power levels. For that, especially for the emerging technology of Gallium Nitride (GaN), in the second section a new approach for power amplifier design will be described, basing on the experimental characterization of the intrinsic Load Line by means of a low frequency high power measurements bench. Thanks to the possibility to develop my Ph.D. in an academic spin-off, MEC – Microwave Electronics for Communications, the results of this activity has been applied to important research programs requested by space agencies, with the aim support the technological transfer from universities to industrial world and to promote a science-based entrepreneurship. For these reasons the proposed design methodology will be explained basing on many experimental results.

Nonlinear constrained and saturated control of power electronics and electromechanical systems

Power electronic converters are extensively adopted for the solution of timely issues, such as power quality improvement in industrial plants, energy management in hybrid electrical systems, and control of electrical generators for renewables. Beside nonlinearity, this systems are typically characterized by hard constraints on the control inputs, and sometimes the state variables. In this respect, control laws able to handle input saturation are crucial to formally characterize the systems stability and performance properties. From a practical viewpoint, a proper saturation management allows to extend the systems transient and steady-state operating ranges, improving their reliability and availability. The main topic of this thesis concern saturated control methodologies, based on modern approaches, applied to power electronics and electromechanical systems. The pursued objective is to provide formal results under any saturation scenario, overcoming the drawbacks of the classic solution commonly applied to cope with saturation of power converters, and enhancing performance. For this purpose two main approaches are exploited and extended to deal with power electronic applications: modern anti-windup strategies, providing formal results and systematic design rules for the anti-windup compensator, devoted to handle control saturation, and “one step” saturated feedback design techniques, relying on a suitable characterization of the saturation nonlinearity and less conservative extensions of standard absolute stability theory results. The first part of the thesis is devoted to present and develop a novel general anti-windup scheme, which is then specifically applied to a class of power converters adopted for power quality enhancement in industrial plants. In the second part a polytopic differential inclusion representation of saturation nonlinearity is presented and extended to deal with a class of multiple input power converters, used to manage hybrid electrical energy sources. The third part regards adaptive observers design for robust estimation of the parameters required for high performance control of power systems.

The market manipulation regime in the European Union

Market manipulation is an illegal practice that enables a person can profit from practices that artificially raise or lower the prices of an instrument in the financial markets. Its prohibition is based on the 2003 Market Abuse Directive in the EU. The current market manipulation regime was broadly considered as a big success except for enforcement and supervisory inconsistencies in the Member States at the initial. A review of the market manipulation regime began at the end of 2007, which became quickly incorporated into the wider EU crisis-era reform program. A number of weaknesses of current regime have been identified, which include regulatory gaps caused by the development of trading venues and financial products, regulatory gaps concerning cross-border and cross-markets manipulation (particular commodity markets), legal uncertainty as a result of various implementation, and inefficient supervision and enforcement. On 12 June 2014, a new regulatory package of market abuse, Market Abuse Regulation and Directive on criminal sanctions for market abuse, has been adopted. And several changes will be made concerning the EU market manipulation regime. A wider scope of the regime and a new prohibition of attempted market manipulation will ensure the prevention of market manipulation at large. The AMPs will be subject to strict scrutiny of ESMA to reduce divergences in implementation. In order to enhance efficiency of supervision and enforcement, powers of national competent authorities will be strengthened, ESMA is imposed more power to settle disagreement between national regulators, and the administrative and criminal sanctioning regimes are both further harmonized. In addition, the protection of fundamental rights is stressed by the new market manipulation regime, and some measures are provided to guarantee its realization. Further, the success EU market manipulation regime could be of significant reference to China, helping China to refine its immature regime.