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.

Silicon nanocrystals tailored for bioimaging and energy conversion

This thesis focus is the development of hybrid organic-inorganic systems based on Silicon Nanocrystals (SiNCs) with possible applications in the field of bioimaging and solar energy conversion. SiNCs were engineered thanks to the realization of a strong covalent Si-C bond on their surface, which allowed us to disperse them in different solvents with different final purpose. Chapter 1 introduces the basic properties of nanomaterials. Chapter 2 describes all the synthetic procedures to obtain the organic molecules-functionalized SiNCs. Chapter 3 illustrates an organic-inorganic antenna system based on SiNCs conjugated with diphenylanthracene (DPA) photoactive molecules, which was also embedded into Luminescent Solar Concentrators (LSC) made of a polymeric matrix. The optical and photovoltaic performances of this device were compared with the ones of a LSC embedded with a physical mixture made of SiNCs plus DPA at the same concentrations of the two components in the covalent system. Chapter 4 shows many different techniques to functionalize SiNCs with polyethylene glycol (PEG) chains in order to make them dispersible in water, for biomedical imaging applications. Chapter 5 presents the synthesis of dyes and/or SiNCs loaded Polymer Nanoparticles (PNPs) capable of excitation energy transfer (EET) mechanism. Chapter 6 is focused on the realization of photo-switchable systems based on azobenzene derivatives-functionalized SiNCs. These organic-inorganic hybrid materials were studied to possibly obtain a new light-driven response of SiNCs. In the end, chapter 7 reports the activity I followed in America, at The University of Texas at Austin, in the laboratory led by the professor Brian Korgel. Here I studied and compared the properties of high temperature hydrosilylated SiNCs and room temperature, radical promoted, hydrosilylated SiNCs.

Nanostructured Systems for Electrocatalysis of Reduction Reactions for Energy Conversion Applications

Oxygen Reduction Reaction (ORR) requires a platinum-based catalyst to reduce the activation barrier. One of the most promising materials as alternative catalysts are carbon-based, graphene and carbon nanotubes (CNT) derivatives. ORR on a carbon-based substrate involves the less efficient two electrons process and the optimal four electrons process. New synthetic strategies to produce tunable graphene-based materials utilizing graphene oxide (GO) as a base inspired the first part of this work. Hydrogen Evolution Reaction (HER) is a slow process requiring also platinum or palladium as catalyst. In the second part of this work, we develop and use a technique for Ni nanoparticles electrodeposition using NiCl2 as precursor in the presence of ascorbate ligands. Electrodeposition of nano-nickel onto flat glassy carbon (GC) and onto nitrogen-doped reduced graphene oxide (rGO-N) substrates are studied. State of the art catalysts for CO2RR requires rare metals rhenium or rhodium. In recent years significant research has been done on non-noble metals and molecular systems to use as electro and photo-catalysts (artificial photosynthesis). As Cu-Zn alloys show good CO2RR performance, here we applied the same nanoparticle electrosynthesis technique using as precursors CuCl2 and Cl2Zn and observed successful formation of the nanoparticles and a notable activity in presence of CO2. Using rhenium complexes as catalysts is another popular approach and di-nuclear complexes have a positive cooperative effect. More recently a growing family of pre-catalysts based on the earth-abundant metal manganese, has emerged as a promising, cheaper alternative. Here we study the cooperative effects of di-nuclear manganese complexes derivatives when used as homogeneous electrocatalysts, as well as a rhenium functionalized polymer used as heterogeneous electrocatalyst.

Molecular and hybrid systems for solar-to-chemical energy conversion

My Ph.D. thesis was dedicated to the exploration of different paths to convert sunlight into the shape of chemical bonds, by the formation of solar fuels. During the past three years, I have focused my research on two of these, namely molecular hydrogen H2 and the reduced nicotinamide adenine dinucleotide enzyme cofactor NAD(P)H. The first could become the ideal energy carrier for a truly clean energy system; it currently represents the best chance to liberate humanity from its dependence on fossil fuels. To address this, I studied different systems which can achieve proton reduction upon light absorption. More specifically, part of my work was aimed to the development of a cost-effective and stable catalyst in combination with a well-known photochemical cycle. To this extent, I worked on transition metal oxides which, as demonstrated in this work, have been identified as promising H2 evolution catalysts, showing excellent activity, stability, and previously unreported versatility. Another branch of my work on hydrogen production dealt with the use of a new class of polymeric semiconductor materials to absorb light and convert it into H2. The second solar fuel mentioned above is a key component of the most powerful methods for chemical synthesis: enzyme catalysis. The high cost of the reduced forms prohibits large-scale utilization, so artificial photosynthetic approaches for regenerating it are being intensively studied. The first system I developed exploits the tremendous reducing properties of a scarcely known ruthenium complex which is able to reduce NAD+. Lastly, I sought to revert the classical role of the sacrificial electron donor to an active component of the system and, to boost the process, I build up an autonomous microfluidic system able to generate highly reproducible NAD(P)H amount, demonstrating the superior performance of microfluidic reactors over batch and representing another successful photochemical NAD(P)H regeneration system.

Physiology and Biotechnology of the Hydrogen Production with the Green Microalga Chlamydomonas reinhardtii

The hydrogen production in the green microalga Chlamydomonas reinhardtii was evaluated by means of a detailed physiological and biotechnological study. First, a wide screening of the hydrogen productivity was done on 22 strains of C. reinhardtii, most of which mutated at the level of the D1 protein. The screening revealed for the first time that mutations upon the D1 protein may result on an increased hydrogen production. Indeed, productions ranged between 0 and more than 500 mL hydrogen per liter of culture (Torzillo, Scoma et al., 2007a), the highest producer (L159I-N230Y) being up to 5 times more performant than the strain cc124 widely adopted in literature (Torzillo, Scoma, et al., 2007b). Improved productivities by D1 protein mutants were generally a result of high photosynthetic capabilities counteracted by high respiration rates. Optimization of culture conditions were addressed according to the results of the physiological study of selected strains. In a first step, the photobioreactor (PBR) was provided with a multiple-impeller stirring system designed, developed and tested by us, using the strain cc124. It was found that the impeller system was effectively able to induce regular and turbulent mixing, which led to improved photosynthetic yields by means of light/dark cycles. Moreover, improved mixing regime sustained higher respiration rates, compared to what obtained with the commonly used stir bar mixing system. As far as the results of the initial screening phase are considered, both these factors are relevant to the hydrogen production. Indeed, very high energy conversion efficiencies (light to hydrogen) were obtained with the impeller device, prooving that our PBR was a good tool to both improve and study photosynthetic processes (Giannelli, Scoma et al., 2009). In the second part of the optimization, an accurate analysis of all the positive features of the high performance strain L159I-N230Y pointed out, respect to the WT, it has: (1) a larger chlorophyll optical cross-section; (2) a higher electron transfer rate by PSII; (3) a higher respiration rate; (4) a higher efficiency of utilization of the hydrogenase; (5) a higher starch synthesis capability; (6) a higher per cell D1 protein amount; (7) a higher zeaxanthin synthesis capability (Torzillo, Scoma et al., 2009). These information were gathered with those obtained with the impeller mixing device to find out the best culture conditions to optimize productivity with strain L159I-N230Y. The main aim was to sustain as long as possible the direct PSII contribution, which leads to hydrogen production without net CO2 release. Finally, an outstanding maximum rate of 11.1 ± 1.0 mL/L/h was reached and maintained for 21.8 ± 7.7 hours, when the effective photochemical efficiency of PSII (ΔF/F'm) underwent a last drop to zero. If expressed in terms of chl (24.0 ± 2.2 µmoles/mg chl/h), these rates of production are 4 times higher than what reported in literature to date (Scoma et al., 2010a submitted). DCMU addition experiments confirmed the key role played by PSII in sustaining such rates. On the other hand, experiments carried out in similar conditions with the control strain cc124 showed an improved final productivity, but no constant PSII direct contribution. These results showed that, aside from fermentation processes, if proper conditions are supplied to selected strains, hydrogen production can be substantially enhanced by means of biophotolysis. A last study on the physiology of the process was carried out with the mutant IL. Although able to express and very efficiently utilize the hydrogenase enzyme, this strain was unable to produce hydrogen when sulfur deprived. However, in a specific set of experiments this goal was finally reached, pointing out that other than (1) a state 1-2 transition of the photosynthetic apparatus, (2) starch storage and (3) anaerobiosis establishment, a timely transition to the hydrogen production is also needed in sulfur deprivation to induce the process before energy reserves are driven towards other processes necessary for the survival of the cell. This information turned out to be crucial when moving outdoor for the hydrogen production in a tubular horizontal 50-liter PBR under sunlight radiation. First attempts with laboratory grown cultures showed that no hydrogen production under sulfur starvation can be induced if a previous adaptation of the culture is not pursued outdoor. Indeed, in these conditions the hydrogen production under direct sunlight radiation with C. reinhardtii was finally achieved for the first time in literature (Scoma et al., 2010b submitted). Experiments were also made to optimize productivity in outdoor conditions, with respect to the light dilution within the culture layers. Finally, a brief study of the anaerobic metabolism of C. reinhardtii during hydrogen oxidation has been carried out. This study represents a good integration to the understanding of the complex interplay of pathways that operate concomitantly in this microalga.

Advanced Waste-To-Energy Cycles

The increase in environmental and healthy concerns, combined with the possibility to exploit waste as a valuable energy resource, has led to explore alternative methods for waste final disposal. In this context, the energy conversion of Municipal Solid Waste (MSW) in Waste-To-Energy (WTE) power plant is increasing throughout Europe, both in terms of plants number and capacity, furthered by legislative directives. Due to the heterogeneous nature of waste, some differences with respect to a conventional fossil fuel power plant have to be considered in the energy conversion process. In fact, as a consequence of the well-known corrosion problems, the thermodynamic efficiency of WTE power plants typically ranging in the interval 25% ÷ 30%. The new Waste Framework Directive 2008/98/EC promotes production of energy from waste introducing an energy efficiency criteria (the so-called “R1 formula”) to evaluate plant recovery status. The aim of the Directive is to drive WTE facilities to maximize energy recovery and utilization of waste heat, in order to substitute energy produced with conventional fossil fuels fired power plants. This calls for novel approaches and possibilities to maximize the conversion of MSW into energy. In particular, the idea of an integrated configuration made up of a WTE and a Gas Turbine (GT) originates, driven by the desire to eliminate or, at least, mitigate limitations affecting the WTE conversion process bounding the thermodynamic efficiency of the cycle. The aim of this Ph.D thesis is to investigate, from a thermodynamic point of view, the integrated WTE-GT system sharing the steam cycle, sharing the flue gas paths or combining both ways. The carried out analysis investigates and defines the logic governing plants match in terms of steam production and steam turbine power output as function of the thermal powers introduced.

Numerical modelling and structural optimization of multifunctional maritime structures aimed to protect harbours and produce energy

The main objective of this PhD thesis is to optimize a specific multifunctional maritime structure for harbour protection and energy production, named Overtopping Breakwater for Energy Conversion (OBREC), developed by the team of the University of Campania. This device is provided with a sloping plate followed by a unique reservoir, which is linked with the machine room (where the energy conversion occurs) by means of a pipe passing through the crown wall, provided with a parapet on top of it. Therefore, the potential energy of the overtopping waves, collected inside the reservoir located above the still water level, is then converted by means of low – head turbines. In order to improve the understanding of the wave – structure interactions with OBREC, several methodologies have been used and combined together: i. analysis of recent experimental campaigns on wave overtopping discharges and pressures at the crown wall on small – scale OBREC cross sections, carried out in other laboratories by the team of the University of Campania; ii. new experiments on cross sections similar to the OBREC device, planned and carried out in the hydraulic lab at the University of Bologna in the framework of this PhD work; iii. numerical modelling with a 1 – phase incompressible fluid model IH – 2VOF, developed by the University of Cantabria, and with a 2 – phase incompressible fluid model OpenFOAM, both available from the literature; iv. numerical modelling with a new 2 – phase compressible fluid model developed in the OpenFOAM environment within this PhD work; v. analysis of the data gained from the monitoring of the OBREC prototype installation.

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Design and fabrication of MOMS-based ultrasonic probes for minimally invasive endoscopic applications

A Micro-opto-mechanical systems (MOMS) based technology for the fabrication of ultrasonic probes on optical fiber is presented. Thanks to the high miniaturization level reached, the realization of an ultrasonic system constituted by ultrasonic generating and detecting elements, suitable for minimally invasive applications or Non Destructive Evaluation (NDE) of materials at high resolution, is demonstrated. The ultrasonic generation is realized by irradiating a highly absorbing carbon film patterned on silicon micromachined structures with a nanosecond pulsed laser source, generating a mechanical shock wave due to the thermal expansion of the film induced by optical energy conversion into heat. The short duration of the pulsed laser, together with an appropriate emitter design, assure high frequency and wide band ultrasonic generation. The acoustic detection is also realized on a MOMS device using an interferometric receiver, fabricated with a Fabry-Perot optical cavity realized by means of a patterned SU-8 and two Al metallization levels. In order to detect the ultrasonic waves, the cavity is interrogated by a laser beam measuring the reflected power with a photodiode. Various issues related to the design and fabrication of these acoustic probes are investigated in this thesis. First, theoretical models are developed to characterize the opto-acoustic behavior of the devices and estimate their expected acoustic performances. Tests structures are realized to derive the relevant physical parameters of the materials constituting the MOMS devices and determine the conditions theoretically assuring the best acoustic emission and detection performances. Moreover, by exploiting the models and the theoretical results, prototypes of acoustic probes are designed and their fabrication process developed by means of an extended experimental activity.

Transport Properties and Novel Sensing Applications of Organic Semiconducting Crystals

The present thesis is focused on the study of Organic Semiconducting Single Crystals (OSSCs) and crystalline thin films. In particular solution-grown OSSC, e.g. 4-hdroxycyanobenzene (4HCB) have been characterized in view of their applications as novel sensors of X-rays, gamma-rays, alpha particles radiations and chemical sensors. In the field of ionizing radiation detection, organic semiconductors have been proposed so far mainly as indirect detectors, i.e. as scintillators or as photodiodes. I first study the performance of 4HCB single crystals as direct X-ray detector i.e. the direct photon conversion into an electrical signal, assessing that they can operate at room temperature and in atmosphere, showing a stable and linear response with increasing dose rate. A dedicated study of the collecting electrodes geometry, crystal thickness and interaction volume allowed us to maximize the charge collection efficiency and sensitivity, thus assessing how OSSCs perform at low operating voltages and offer a great potential in the development of novel ionizing radiation sensors. To better understand the processes generating the observed X-ray signal, a comparative study is presented on OSSCs based on several small-molecules: 1,5-dinitronaphthalene (DNN), 1,8-naphthaleneimide (NTI), Rubrene and TIPS-pentacene. In addition, the proof of principle of gamma-rays and alpha particles has been assessed for 4HCB single crystals. I have also carried out an investigation of the electrical response of OSSCs exposed to vapour of volatile molecules, polar and non-polar. The last chapter deals with rubrene, the highest performing molecular crystals for electronic applications. We present an investigation on high quality, millimeter-sized, crystalline thin films (10 – 100 nm thick) realized by exploiting organic molecular beam epitaxy on water-soluble substrates. Space-Charge-Limited Current (SCLC) and photocurrent spectroscopy measurements have been carried out. A thin film transistor was fabricated onto a Cytop® dielectric layer. The FET mobility exceeding 2 cm2/Vs, definitely assess the quality of RUB films.

Photophysics of Carbon Nanotubes: from Dispersion to Supramolecular Systems

The aim of this PhD thesis is the investigation of the photophysical properties of materials that can be exploited in solar energy conversion. In this context, my research was mainly focused on carbon nanotube-based materials and ruthenium complexes. The first part of the thesis is devoted to carbon nanotubes (CNT), which have unique physical and chemical properties, whose rational control is of substantial interest to widen their application perspectives in many fields. Our goals were (i) to develop novel procedures for supramolecular dispersion, using amphiphilic block copolymers, (ii) to investigate the photophysics of CNT-based multicomponent hybrids and understand the nature of photoinduced interactions between CNT and selected molecular systems such as porphyrins, fullerenes and oligo (p-phynylenevinylenes). We established a new protocol for the dispersion of SWCNTs in aqueous media via non-covalent interactions and demonstrated that some CNT-based hybrids are suitable for testing in PV devices. The second part of the work is focussed on the study of homoleptic and heteroleptic Ru(II) complexes with bipyridine and extended phenanthroline ligands. Our studies demonstrated that these compounds are potentially useful as light harvesting systems for solar energy conversion. Both CNT materials and Ru(II) complexes have turned out to be remarkable examples of photoactive systems. The morphological and photophysical characterization of CNT-based multicomponent systems allowed a satisfactory rationalization of the photoinduced interactions between the individual units, despite several hurdles related to the intrinsic properties of CNTs that prevent, for instance, the utilization of laser spectroscopic techniques. Overall, this work may prompt the design and development of new functional materials for photovoltaic devices.

Nanocarbon-Supported Electrocatalysts for the Alkaline Water Splitting and Fuel Cells

Electrocatalysts play a significant role in the processes of electrochemical energy conversion. This thesis focuses on the preparation of carbon-supported nanomaterials and their application as electrocatalysts for alkaline water electrocatalysis and fuel cell. A general synthetic route was developed, i.e., species intercalate into carbon layers of graphite forming graphite intercalation compound, followed by dispersion producing graphenide solution, which then as reduction agent reacts with different metal sources generating the final materials. The first metal precursor used was non-noble metal iron salt, which generated iron (oxide) nanoparticles finely dispersed on carbon layers in the final composite materials. Meanwhile, graphite starting materials differing in carbon layer size were utilized, which would diversify corresponding graphenide solutions, and further produce various nanomaterials. The characterization results showed that iron (oxide) nanoparticles varying in size were obtained, and the size was determined by the starting graphite material. It was found that they were electrocatalytically active for oxygen reactions. In particular, the one with small iron (oxide) nanoparticles showed excellent electrocatalytic activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Afterwards, the metal precursor was tuned from non-noble metal salt to noble metal salt. It was confirmed that carbon-supported Rh, Pt, and RhPt (oxide) nanoparticle composite materials were also successfully obtained from the reaction between graphenide solution and corresponding noble metal precursor. The electrochemical measurements showed that the prepared noble metal-based nanomaterials were quite effective for hydrogen evolution reaction (HER) electrocatalysis, and the Rh sample could also display excellent electrocatalytic property towards OER. Moreover, by this synthetic approach carbon-supported noble metal Pt and non-noble metal nickel (Ni) composite material was also prepared. Therefore, the utilization efficiency of noble metal could be improved. The prepared NiPt sample displayed a property close to benchmark HER electrocatalyst.

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.

Planning and flexible operation of storage systems in power grids: from transmission to distribution networks

The first part of the thesis has been devoted to the transmission planning with high penetration of renewable energy sources. Both stationary and transportable battery energy storage (BES, BEST) systems have been considered in the planning model, so to obtain the optimal set of BES, BEST and transmission lines that minimizes the total cost in a power network. First, a coordinated expansion planning model with fixed transportation cost for BEST devices has been presented; then, the model has been extended to a planning formulation with a distance-dependent transportation cost for the BEST units, and its tractability has been proved through a case study based on a 190-bus test system. The second part of this thesis is then devoted to the analysis of planning and management of renewable energy communities (RECs). Initially, the planning of photovoltaic and BES systems in a REC with an incentive-based remuneration scheme according to the Italian regulatory framework has been analysed, and two planning models, according to a single-stage, or a multi-stage approach, have been proposed in order to provide the optimal set of BES and PV systems allowing to achieve the minimum energy procurement cost in a given REC. Further, the second part of this thesis is devoted to the study of the day-ahead scheduling of resources in renewable energy communities, by considering two types of REC. The first one, which we will refer to as “cooperative community”, allows direct energy transactions between members of the REC; the second type of REC considered, which we shall refer to as “incentive-based”, does not allow direct transactions between members but includes economic revenues for the community shared energy, according to the Italian regulation framework. Moreover, dispatchable renewable energy generation has been considered by including producers equipped with biogas power plants in the community.

Innovative photoresponsive materials & supramolecular structures

This thesis focuses on two main topics: photoresponsive azobenzene-based polymers and supramolecular systems generated by the self-assembly of lipophilic guanosines. In the first chapters describe innovative photoresponsive devices and materials capable of performing multiple roles in the field of soft robotics and energy conversion. Chapter 2 describes a device obtained by coupling a photoresponsive liquid-crystalline network and a piezoelectric polymer to convert visible light into electricity. Chapter 3 deals with a material that can assume different shapes when triggered by three different stimuli in different environments. Chapter 4 reports a highly performing artificial muscle that contracts when irradiated. The last two chapters report on supramolecular structures generated from functionalized guanosines dissolved in organic solvents. Chapter 6 illustrates the self-assembly into G-quadruplexes of 8- and 5’-functionalized guanosines in the absence of templating ions. Chapter 7 describes the supramolecular structure generated by the assembly of a lipophilic guanosine in the presence of silver cations. Chapter 6 is reproduced from an already published paper, while the other chapters are going to be submitted to different journals in a couple of months.