ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

ELECTRON TRANSPORT IN LOW-DIMENSIONAL NANOSTRUCTURES - THEORETICAL STUDY WITH APPLICATION

Graphene as a carbon monolayer has attracted extensive research interest in recent years. My research work within the frame of density functional theory has suggested that positioning graphene in proximity to h-BN may induce a finite energy gap in graphene, which is important for device applications. For an AB-stacked graphene/BN bilayer, a finite gap is induced at the equilibrium configuration. This induced gap shows a linear relationship with the applied strain. For a graphene/BN/graphene trilayer, a negligible gap is predicted in the ground state due to the overall symmetry of the system. When an electric field is applied, a tunable gap can be obtained for both AAA and ABA stackings. Enhanced tunneling current in the AA-stacked bilayer nanoribbons is predicted compared to either single-layer or AB-stacked bilayer nanoribbons. Interlayer separation between the nanoribbons is shown to have a profound impact on the conducting features. The effect of boron or nitrogen doping on the electronic transport properties of C60 fullerene is studied. The BC59 fullerene exhibits a considerably higher current than the pristine or nitrogen doped fullerenes beyond the applied bias of 1 V, suggesting it can be an effective semiconductor in p-type devices. The interaction between nucleic acid bases - adenine (A), guanine (G), cytosine (C), thymine (T) and uracil (U) - and a hydrogen-passivated silicon nanowire (SiNW) is investigated. The binding energy of the bases with the SiNW shows the order: G > A~C~T~U. This suggests that the interaction strength of a hydrogen passivated SiNW with the nucleic acid bases is nearly the same-G being an exception. The nature of the interaction is suggested to be electrostatic.

Disorder-induced light localisation:from random to artificial

Light localisation in one-dimensional (1D) randomly disordered medium is usually characterized by randomly distributed resonances with fluctuating transmission values, instead of selectively distributed resonances with close-to-unity transmission values that are needed in real application fields. By a resonance tuning scheme developed recently, opening of favorable resonances or closing of unfavorable resonances are achieved by disorder micro-modification, both on the layered medium and the fibre Bragg grating (FBG) array. And furthermore, it is shown that those disorder-induced resonances are independently tunable. Therefore, selected resonances and arranged light localisation can be achieved via artificial disorder, and thus meet the demand of various application fields.

Weakly-constrained codes for suppression of patterning effects in digital communications

We propose weakly-constrained stream and block codes with tunable pattern-dependent statistics and demonstrate that the block code capacity at large block sizes is close to the the prediction obtained from a simple Markov model published earlier. We demonstrate the feasibility of the code by presenting original encoding and decoding algorithms with a complexity log-linear in the block size and with modest table memory requirements. We also show that when such codes are used for mitigation of patterning effects in optical fibre communications, a gain of about 0.5dB is possible under realistic conditions, at the expense of small redundancy (≈10%). © 2010 IEEE

Study of the Electrochemical, Physical and Morphological Characteristics of Anode Catalysts for Perfluorosulfonic Acid (PFSA) Membrane Water Electrolysers

A number of supported and un-supported Oxygen Evolution Reaction (OER) iridium based electrocatalysts for Polymer Electrolyte Membrane Water Electrolysis (PEMWE) were synthesized using a polyol method. The electrocatalysts and the supports were characterized using a wide range of physical and electrochemical characterization methods. The effect of morphological characteristics of the OER electrocatalyst and the support on the OER activity was studied. The results of this thesis contribute to the existing research to reduce the cost of PEMWE by enhancing the utilization of precious metal for OER electrocatalysis. Iridium electrocatalysts supported on antimony tin oxide (Ir/ATO) were synthesized using the polyol method with two different heating techniques: conventional and microwave-irradiation. It was shown that the physical morphology and electrochemical properties of Ir/ATO synthesized with the two heating methods were comparable. However, the microwave irradiation method was extremely faster than the conventional heating method. Additionally, the effect of heat treatment (calcination temperature) on the morphology and OER activity of Ir/ATO synthesized electrocatalyst with the conventional polyol method. It was found that the iridium electrocatalyst synthesized with the polyol method, consisted of 1-5 nm particles, possessed an amorphous structure, and contained iridium with an average oxidation state of less than +4. Calcining the catalyst at temperatures more than 400 ºC and less than 700ºC: 1) increased the size of the iridium particles to 30 nm, 2) changed the structure of iridium particles from amorphous to crystalline, 3) increased the iridium oxidation state to +4 (IrO2), 4) reduced the electrochemically active surface area by approximately 50%, and 5) reduced the OER activity by approximately 25%; however, it had no significant effect on the physical and chemical morphology of the ATO support. Moreover, potential support metal carbides and oxides including: Tantalum Carbide (TaC), Niobium Oxide (Nb2O5), Niobium Carbide (NbC), Titanium Carbide (TiC), Tungsten Carbide (WC) and Antimony-doped Tin Oxide (ATO, Sb2O5-SnO2), were characterized, and used as support for the iridium OER electrocatalysts. TaC was found to be a promising support, and increasing its surface area by 4% improved the OER performance of the final supported catalyst by approximately 50%.

Influence of combined fundamental potentials in a nonlinear vibration energy harvester

Ambient mechanical vibrations have emerged as a viable energy source for low-power wireless sensor nodes aiming the upcoming era of the ‘Internet of Things’. Recently, purposefully induced dynamical nonlinearities have been exploited to widen the frequency spectrum of vibration energy harvesters. Here we investigate some critical inconsistencies between the theoretical formulation and applications of the bistable Duffing nonlinearity in vibration energy harvesting. A novel nonlinear vibration energy harvesting device with the capability to switch amidst individually tunable bistable-quadratic, monostable-quartic and bistable-quartic potentials has been designed and characterized. Our study highlights the fundamentally different large deflection behaviors of the theoretical bistable-quartic Duffing oscillator and the experimentally adapted bistable-quadratic systems, and underlines their implications in the respective spectral responses. The results suggest enhanced performance in the bistable-quartic potential in comparison to others, primarily due to lower potential barrier and higher restoring forces facilitating large amplitude inter-well motion at relatively lower accelerations.

Activated carbons with high nitrogen content by a combination of hydrothermal carbonization with activation

This paper reports the production of carbons materials with a nitrogen content around 8%(w/w) and a well-developed porous structure, with BET surface area and pore volume up to 2130 m2 g−1 and 1.12 cm3 g−1, respectively, produced by a combination of hydrothermal carbonization, an environmental friendly method in the production of sustainable tunable carbon materials, with traditional activation methods. The porosity was developed through an activation process according to different routes, namely activation with CO2 and chemical activation using CaCO3 and K2CO3. The successful production of activated carbons using chitosan as a nitrogen source revealed to be a good alternative to post-synthesis methods.

Resonant metamaterials for the control of Rayleigh waves

Since their emergence, locally resonant metamaterials have found several applications for the control of surface waves, from micrometer-sized electronic devices to meter-sized seismic barriers. The interaction between Rayleigh-type surface waves and resonant metamaterials has been investigated through the realization of locally resonant metasurfaces, thin elastic interfaces constituted by a cluster of resonant inclusions or oscillators embedded near the surface of an elastic waveguide. When such resonant metasurfaces are embedded in an elastic homogeneous half-space, they can filter out the propagation of Rayleigh waves, creating low-frequency bandgaps at selected frequencies. In the civil engineering context, heavy resonating masses are needed to extend the bandgap frequency width of locally resonant devices, a requirement that limits their practical implementations. In this dissertation, the wave attenuation capabilities of locally resonant metasurfaces have been enriched by proposing (i) tunable metasurfaces to open large frequency bandgaps with small effective inertia, and by developing (ii) an analytical framework aimed at studying the propagation of Rayleigh waves propagation in deep resonant waveguides. In more detail, inertial amplified resonators are exploited to design advanced metasurfaces with a prescribed static and a tunable dynamic response. The modular design of the tunable metasurfaces allows to shift and enlarge low-frequency spectral bandgaps without modifying the total inertia of the metasurface. Besides, an original dispersion law is derived to study the dispersive properties of Rayleigh waves propagating in thick resonant layers made of sub-wavelength resonators. Accordingly, a deep resonant wave barrier of mechanical resonators embedded inside the soil is designed to impede the propagation of seismic surface waves. Numerical models are developed to confirm the analytical dispersion predictions of the tunable metasurface and resonant layer. Finally, a medium-size scale resonant wave barrier is designed according to the soil stratigraphy of a real geophysical scenario to attenuate ground-borne vibration.

Ossidazione elettrocatalitica di glucosio su schiume di nickel per la produzione selettiva di acido gluconico e acido glucarico

The selective electro-oxidation of D-glucose represents a promising way for the synthesis of many platform molecules, currently produced from non-renewable fossil fuels. Electrocatalysis is gaining considerable interest as an alternative to the thermochemical process, since it allows the process to be sustainable by operating at room temperature and pressure as well as using green solvents and electricity produced from renewable sources. In this work, the activity of three electrocatalysts, based on open cell Ni foams, towards the electrochemical oxidation of glucose to gluconic acid and glucaric acid was initially compared: a Ni bare foam, and Ni foams calcined at 500 °C for one hour and electrodeposited with Ni NP nanoparticles. The calcined foam turned out to be the most efficient. Then, the performance of this Ni calcined electrocatalyst was studied varying the reaction conditions, such as the potential applied (from 0,5V to 1,0V vs SCE), D-glucose concentration (0,01M, 0,05M and 0,10M) and NaOH concentration (0,10M and 1,0M). The activity of the electrocatalysts was evaluated in terms of glucose conversion, gluconic and gluconic acid selectivity and faradic efficiency. The best results were obtained over a Ni calcined foam with a 0,05M solution of D-glucose and 0,10M of NaOH at a 0,80V vs SCE potential.

Defect states in MAPbBr3 by photo-induced current transient spectroscopy

In the past decade, perovskites have been under the spotlight as promising semicon- ductors with unique properties. Hybrid halide perovskites show excellent characteristic properties suitable for optoelectronic applications as tunable band gap, high absorption coefficient, large mobility and long carrier recombination lifetime. However, a complete understanding of environmental instability and the nature of defects in these materials is still lacking, hindering the development of perovskite-based technologies. In this work we studied MAPbBr3 single crystals, fabricated with Inverse Temperature Crystallization (ITC) technique, with Photo-Induced Current Transient Spectroscopy (PICTS). PICTS is a transient photocurrent measurement rarely employed for studying perovskites mate- rials, that allows for the defects characterization in high resistivity materials. We studied the samples under different conditions, such as negative and positive voltage biases, bias stress, different contact geometries and different illumination wavelengths, in order to study their effect on the material physical properties and to evaluate the trap activation energies and their behavior under different working conditions.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

Drive up electrochemical and electrochemiluminescence signal through biosensing mechanism optimization

Biomarkers are biological indicators of human health conditions. Their ultra-sensitive quantification is of cardinal importance in clinical monitoring and early disease diagnosis. Biosensors are some worldwide simple and easy-to-use analytical devices as a matter of fact, biosensors using electrochemiluminescence (ECL) are one of the most promising biosensors that needs an ever-increasing sensitivity for improving its clinical effectiveness. The principal aspiration of this project is the investigation of the ECL generation mechanisms for enhancing the ECL intensity and the development of an ultrasensitive sensor, the use of metal-oxide materials (Mox) and the substitution of metal-free dyes. Novel dyes such as BODIPY, TADF are used to improve the sensitivity of ECL techniques thanks to their advantageous and tunable properties, enhancing the signal and also the ECL efficiency. Additionally, the use of Mox could be beneficial for the investigation of two different ECL mechanisms, which occur simultaneously. In this thesis, the investigation of size and distance effects on electrochemical (EC) mechanisms was carried out through the innovative combination of a standard detection system using different size of micromagnetic beads (MBs). That allowed the discovery of an unexpected and highly efficient mechanistic path for electrochemical generation at small distances from the electrode’s surface. The smallest MBs (0.1μm) demostrate an enhancement of electrochemical signal than the bigger one (2.8μm) until 4 times of magnitude. Finally, a novel ultrasensitive sensor, based on the coreactant-luminophores mechanism, was developed for the determination of whole viral genome specific for cardiac HBV and COVID-19 virus. In conclusion, the ECL and the use of EC techniques (such as amperometry), improved the understanding of mechanisms responsible for the ECL/EC signal led to a great enhancement in the signal.

Modelling the influence of diradical character and aggregation on conjugated molecular materials

Molecular materials are made by the assembly of specifically designed molecules to obtain bulk structures with desired solid-state properties, enabling the development of materials with tunable chemical and physical properties. These properties result from the interplay of intra-molecular constituents and weak intermolecular interactions. Thus, small changes in individual molecular and electronic structure can substantially change the properties of the material in bulk. The purpose of this dissertation is, thus, to discuss and to contribute to the structure-property relationships governing the electronic, optical and charge transport properties of organic molecular materials through theoretical and computational studies. In particular, the main focus is on the interplay of intra-molecular properties and inter-molecular interactions in organic molecular materials. In my three-years of research activity, I have focused on three major areas: 1) the investigation of isolated-molecule properties for the class of conjugated chromophores displaying diradical character which are building blocks for promising functional materials; 2) the determination of intra- and intermolecular parameters governing charge transport in molecular materials and, 3) the development and application of diabatization procedures for the analysis of exciton states in molecular aggregates. The properties of diradicaloids are extensively studied both regarding their ground state (diradical character, aromatic vs quinoidal structures, spin dynamics, etc.) and the low-lying singlet excited states including the elusive double-exciton state. The efficiency of charge transport, for specific classes of organic semiconductors (including diradicaloids), is investigated by combining the effects of intra-molecular reorganization energy, inter-molecular electronic coupling and crystal packing. Finally, protocols aimed at unravelling the nature of exciton states are introduced and applied to different molecular aggregates. The role of intermolecular interactions and charge transfer contributions in determining the exciton state character and in modulating the H- to J- aggregation is also highlighted.

Non-linear modelling of microwave devices embedding nano-ferroelectric materials for real-time reconfigurable transmitarray

In this thesis work a nonlinear model for Interdigitated Capacitors (IDCs) based on ferroelectric materials, is proposed. Through the properties of materials such as Hafnium-Zirconium Oxide (HfZrO2), it is possible to realize tunable radiofrequency (RF) circuits. In particular, the model proposed in this thesis describes the use of an IDC, realized on a High-Resistivity silicon substrate, as a phase shifter for beam-steering applications. The model is obtained starting from already present experimental measurements, through which it is possible to identify a circuit model. The model is tested for both low power values and other power values using Harmonic Balance simulations, which show an excellent convergence of the model up to 40 dBm of input power. Furthermore, an array composed by two patches operating both at 2.55 GHz, which exploits the tunable properties of the HfZrO-based IDC is proposed. At 0dBm the model shows a 47° phase shift with polarization -1 V and 1 V which leads to a 11° steering of the main lobe of the array.

Competition between boson condensation and molecule formation in 2D Bose-Fermi mixtures with a pairing interaction

The study of ultra-cold atomic gases is one of the most active field in contemporary physics. The main motivation for the interest in this field consists in the possibility to use ultracold gases to simulate in a controlled way quantum many-body systems of relevance to other fields of physics, or to create novel quantum systems with unusual physical properties. An example of the latter are Bose-Fermi mixtures with a tunable pairing interaction between bosons and fermions. In this work, we study with many-body diagrammatic methods the properties of this kind of mixture in two spatial dimensions, extending previous work for three dimensional Bose-Fermi mixtures. At zero temperature, we focus specifically on the competition between boson condensation and the pairing of bosons and fermions into molecules. By a numerical solution of the main equations resulting by our many-body diagrammatic formalism, we calculate and present results for several thermodynamic quantities of interest. Differences and similarities between the two-dimensional and three-dimensional cases are pointed out. Finally, our new results are applied to discuss a recent proposal for creating a p-wave superfluid in Bose-Fermi mixtures with the fermionic molecules which form for sufficiently strong Bose-Fermi attraction.