Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.

Humified fraction of organic matter due to plant mixture cultivation.

The aim of this study was to assess the organic matter changes in quantity and quality, particularly of the humic fraction in the surface layer (0?20 cm), of a Typic Plinthustalf soil under different management of plant mixtures used as green manure for mango (Mangifera indica L.) crops. The plant mixtures, which were seeded between rows of mango trees, were formed by two groups of leguminous and non -leguminous plants. Prior to sowing, seeds were combined in different proportions and compositions constituting the following treatments: 100% non-leguminous species (NL); 100% leguminous species (L); 75% L and 25% NL; 50% L and 50% NL; 25% L and 75% NL; and 100% spontaneous vegetation, considered a control. The plant mixtures that grew between rows of mango trees caused changes in the chemical composition of the soil organic matter, especially for the treatments 50% L and 50% NL and 25% L and 75% NL, which increased the content of humic substances in the soil organic matter. However, the treatment 25% L and 75% NL was best at minimising loss of total organic carbon from the soil. The humic acids studied have mostly aliphatic characteristics, showing large amounts of carboxylic and nitrogen groups and indicating that most of the organic carbon was formed by humic substances, with fulvic acid dominating among the alkali soluble fractions.

Mode-I fracture parameters of quasi-brittle materials: direct evaluation using DIC and relationship with Mode-II interfacial parameters

The objective of this thesis is the investigation of the Mode-I fracture mechanics parameters of quasi-brittle materials to shed light onto the influence of the width and size of the specimen on the fracture response of notched beams. To further the knowledge on the fracture process, 3D digital image correlation (DIC) was employed. A new method is proposed to determine experimentally the critical value of the crack opening, which is then used to determine the size of the fracture process zone (FPZ). In addition, the Mode-I fracture mechanics parameters are compared with the Mode-II interfacial properties of composites materials that feature as matrices the quasi-brittle materials studied in Mode-I conditions. To investigate the Mode II fracture parameters, single-lap direct shear tests are performed. Notched concrete beams with six cross-sections has been tested using a three-point bending (TPB) test set-up (Mode-I fracture mechanics). Two depths and three widths of the beam are considered. In addition to concrete beams, alkali-activated mortar beams (AAMs) that differ by the type and size of the aggregates have been tested using the same TPB set-up. Two dimensions of AAMs are considered. The load-deflection response obtained from DIC is compared with the load-deflection response obtained from the readings of two linear variable displacement transformers (LVDT). Load responses, peak loads, strain profiles along the ligament from DIC, fracture energy and failure modes of TPB tests are discussed. The Mode-II problem is investigated by testing steel reinforced grout (SRG) composites bonded to masonry and concrete elements under single-lap direct shear tests. Two types of anchorage systems are proposed for SRG reinforced masonry and concrete element to study their effectiveness. An indirect method is proposed to find the interfacial properties, compare them with the Mode-I fracture properties of the matrix and to model the effect of the anchorage.

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.

Valorization of bio-alcohols into added value chemicals

The present research work focused on the valorisation and upgrading of bio-ethanol over heterogeneous catalysts in a lab-scale continuous gas-flow system. In the Unibo laboratories, catalytic tests have been carried out in the temperature range 300-600°C by feeding an ethanol/He mixture in the reactor. After choosing the reaction conditions, ion-exchanged hydroxyapatite with transition metals (i.e., Fe, Cu) and alkaline earth metal (i.e., Sr) have been synthesized and tested. The Sr-HAP catalyst led to the formation of a complex reaction mixture the composition of which need further optimization in order to fill the requisite to be used as fuel-blend. Then, some zirconium-oxide based catalysts have been prepared through two different methods, precipitation and hydrothermal, by varying some synthetic parameters (i.e., pH, the nature of the base) and by adding a transition metal as dopant agent (i.e., Ti and Y). The presence of a dopant into the zirconia structure favoured the stabilization of the tetragonal or cubic phase against the monoclinic one. Interestingly, 5%mol Ti-doped zirconia exhibited a different catalytic behaviour yielding diethyl ether as major product at 300°C, while all the others samples produced mainly ethylene. Then, the effect of acid-base properties of sepiolite, using alkali metals (i.e., Na, K, Cs) with different metal loading (i.e., 2, 4, 5, 7, 14 wt%) as promoters, and of the redox properties of sepiolite-supported CuO or NiO, on the catalytic conversion of ethanol into n-butanol has been investigated. Thermal treated sepiolite samples mainly acted as acid catalyst, yielding preferentially the dehydration products of ethanol (ethylene and diethyl ether). Best results in terms of activity (ethanol conversion, 59%) and n-butanol selectivity (30%) where obtained at 400ºC and a contact time, W/F, of 2 g/mL·s over the catalyst consisting of sepiolite calcined at 500ºC modified with 7 wt% of cesium.

Synthesis and characterization of prussian blue analogue materials for post-Li ion batteries

Energy issues have always been a subject of concern to people. During the past 30 years, rechargeable Li-ion batteries (LIBs) have been widely used in portable electronic devices and power tools because of their high energy density and efficiency among practical secondary batteries. While the unevenly distribution of Lithium sources and the increasing cost of lithium-raw material can not satisfy the requirement for further cost reduction, especially for the grid-scale energy storage. Post-lithium ion batteries as promising replacement for LIBs have attracted wide attention, owing to their high abundant resources and adequate insertion potential. Similar with Li-ion batteries, finding a suitable electrode material is the key for the research and application of the post-Li ion batteries. In our project, we focus our study on Prussian blue analogues (PBAs), with formula AxM[M’(CN)6]1-y□y•zH2O (0≤x≤2, 0alkali-metal ion, M and M’ are transition metal ions, □ represents the M’(CN)6 vacancy, which are archetype of metal-organic framework, with 3D frameworks which allow for a facile insertion/ extraction of ions with negligible lattice strain. By substituting the metal sites with different transition metals, we can get a series of compounds that can be used as both cathode and anode material for both Li-ion and post-Li batteries. The most commonly studied PBAs are metal haxacyanoferrate, with the carbon-sites of -CN- ligands fix connected with Fe. Here, we synthesized three different PBAs: manganese hexacynoferrate (MnHCF), zinc hexacynoferrate (ZnHCF) and titanium hexacynoferrate (TiHCF), using co-precipitation method, and their electrochemical properties were tested in both aqueous Na+, K+, Mg2+, Zn2+ and organic Li+, Na+ electrolytes. Various X-ray techniques were employed to study their electronic and structural properties of electrodes and electrochemical reaction mechanism during cycling.

Geopolymers for tile industry

This project aims to develop energy-saving methods for manufacturing tiles by using geopolymerization as an innovative processing technique. In fact, classical ceramic tiles are usually produced by sintering at temperatures ranging between 1100-1250 °C depending on natural raw materials selected for the mixture. Geopolymers, instead, are amorphous aluminosilicate inorganic polymers obtained by mixing alkali-silicate solutions with reactive aluminosilicate precursors, and geopolymerization may occur at room temperature or at temperature lower than 150 °C, and several types of waste may be used as geopolymer precursors. The possibility to obtain geopolymer tiles with properties comparable with those of ceramic tiles is extremely challenging, but geopolymerization would represent a huge energy-saving in the consolidation process as well as in natural raw materials exploitation.

Polymerization of isatin towards polymers for anion exchange membranes and gas separation applications

In a world where the problem of energy resources, pollution and all aspects related to these issues become more and more dominant, a greater commitment is needed in the search for solutions. The goal of this project is to make a contribution to the research and development of new materials to reduce the environmental impact in some fields. First of all, we tried to synthesize and prepare an isatin-based membrane which has the potential for use in separating industrial gases. Furthermore, ion exchange membranes, specifically hydroxide exchange membranes (HEMs) derived from the same product can be developed for fuel cells (HEMFC) applications. These materials are essential for energy conversion and storage. The most difficult challenge is to guarantee their thermal stability and stability in corrosive environments such as alkali without losing efficiency. In recent years the poly- hydroxyalkylation catalysed with superacids, e.g. TFSA, has become increasingly studied. This reaction is exploited for the synthesis of the compounds of this thesis. After a preliminary optimization of the reaction conditions it was concluded that due to the rigidity and excessive reactivity of the system, it was not possible to obtain the isatin-based membrane to evaluate the gas separation properties. The synthesis of precursor materials for HEMs was successful by using 1-(4-bromobutyl)indoline-2,3-dione (BID) instead of isatin. A characterization of the obtained polymers was carried out using NMR, TGA and DSC analyses, and subsequently the membranes were functionalized with different ammonium-based cations. Unfortunately, this last step was not successful due to the appearance of side reactions. Future studies on the mechanism and kinetics of the reaction solve this obstacle.

Characterization of in-gap electronic states in two-dimensional single crystal PEA2PbBr4 perovskite for X-ray detection

Hybrid Organic-Inorganic Halide Perovskites (HOIPs) include a large class of materials described with the general formula ABX3, where A is an organic cation, B an inorganic cation and X an halide anion. HOIPs show excellent optoelectronic characteristics such as tunable band gap, high adsorption coefficient and great mobility life-time. A subclass of these materials, the so-called two- dimensional (2D) layered HOIPs, have emerged as potential alternatives to traditional 3D analogs to enhance the stability and increase performance of perovskite devices, with particular regard in the area of ionizing radiation detectors, where these materials have reached truly remarkable milestones. One of the key challenges for future development of efficient and stable 2D perovskite X-ray detector is a complete understanding of the nature of defects that lead to the formation of deep states. Deep states act as non-radiative recombination centers for charge carriers and are one of the factors that most hinder the development of efficient 2D HOIPs-based X-ray detectors. In this work, deep states in PEA2PbBr4 were studied through Photo-Induced Current Transient Spectroscopy (PICTS), a highly sensitive spectroscopic technique capable of detecting the presence of deep states in highly resistive ohmic materials, and characterizing their activation energy, capture cross section and, under stringent conditions, the concentration of these states. The evolution of deep states in PEA 2 PbBr 4 was evaluated after exposure of the material to high doses of ionizing radiation and during aging (one year). The data obtained allowed us to evaluate the contribution of ion migration in PEA2PbBr4. This work represents an important starting point for a better understanding of transport and recombination phenomena in 2D perovskites. To date, the PICTS technique applied to 2D perovskites has not yet been reported in the scientific literature.