Charge accumulation and transport in degenerately doped semiconducting polymers with mixed ionic and electronic conductivity

This thesis is part of the fields of Material Physics and Organic Electronics and aims to determine the charge carrier density and mobility in the hydrated conducting polymer–polyelectrolyte blend PEDOT:PSS. This kind of material combines electronic semiconductor functionality with selective ionic transport, biocompatibility and electrochemical stability in water. This advantageous material properties combination makes PEDOT:PSS a unique material to build organic electrochemical transistors (OECTs), which have relevant application as amplifying transducers for bioelectronic signals. In order to measure charge carrier density and mobility, an innovative 4-wire, contact independent characterization technique was introduced, the electrolyte-gated van der Pauw (EgVDP) method, which was combined with electrochemical impedance spectroscopy. The technique was applied to macroscopic thin film samples and micro-structured PEDOT:PSS thin film devices fabricated using photolithography. The EgVDP method revealed to be effective for the measurements of holes’ mobility in hydrated PEDOT:PSS thin films, which resulted to be <μ>=(0.67±0.02) cm^2/(V*s). By comparing this result with 2-point-probe measurements, we found that contact resistance effects led to a mobility overestimation in the latter. Ion accumulation at the drain contact creates a gate-dependent potential barrier and is discussed as a probable reason for the overestimation in 2-point-probe measurements. The measured charge transport properties of PEDOT:PSS were analyzed in the framework of an extended drift-diffusion model. The extended model fits well also to the non-linear response in the transport characterization and results suggest a Gaussian DOS for PEDOT:PSS. The PEDOT:PSS-electrolyte interface capacitance resulted to be voltage-independent, confirming the hypothesis of its morphological origin, related to the separation between the electronic (PEDOT) and ionic (PSS) phases in the blend.

Sintesi e caratterizzazione di nanoparticelle di ossido di stagno dopate

In the last years, new materials have been developed in the broad area of nanoscience. Among them, an emergent class characterized by excellent electrical conductivity properties as well as high optical transmittance in the visible region are TCOs (Transparent Conducting Oxides). Due to their versatile properties, they have found many applications in a lot of optoelectronic devices, such as solar cells, liquid crystal displays, touch-panel displays, gas sensors, to cite a few examples. Different research groups have studied and characterized the TCOs. In this context, a new synthetic method has been developed to produce FTO nanocrystals (Fluorine-doped Tin Oxide NCs) in Prof. Pinna’s lab at the Humboldt University in Berlin. FTO belongs to the TCO category, and they have been studied as a promising alternative to ITO NCs (Indium Tin Oxide) which represent the standard TCO material in terms of properties and performances. In this work, FTO NCs have been synthesized using the “benzyl alcohol route” (a non-aqueous sol-gel method) via microwave, which permits to produce FTO particles with good properties as revealed by the characterizations performed, employing a cheap, fast and clean method.

Anaerobic oxidation of ethanol over spinel mixed oxides: the first step in the steam-iron process for H2 production

The future hydrogen demand is expected to increase, both in existing industries (including upgrading of fossil fuels or ammonia production) and in new technologies, like fuel cells. Nowadays, hydrogen is obtained predominantly by steam reforming of methane, but it is well known that hydrocarbon based routes result in environmental problems and besides the market is dependent on the availability of this finite resource which is suffering of rapid depletion. Therefore, alternative processes using renewable sources like wind, solar energy and biomass, are now being considered for the production of hydrogen. One of those alternative methods is the so-called “steam-iron process” which consists in the reduction of a metal-oxide by hydrogen-containing feedstock, like ethanol for instance, and then the reduced material is reoxidized with water to produce “clean” hydrogen (water splitting). This kind of thermochemical cycles have been studied before but currently some important facts like the development of more active catalysts, the flexibility of the feedstock (including renewable bio-alcohols) and the fact that the purification of hydrogen could be avoided, have significantly increased the interest for this research topic. With the aim of increasing the understanding of the reactions that govern the steam-iron route to produce hydrogen, it is necessary to go into the molecular level. Spectroscopic methods are an important tool to extract information that could help in the development of more efficient materials and processes. In this research, ethanol was chosen as a reducing fuel and the main goal was to study its interaction with different catalysts having similar structure (spinels), to make a correlation with the composition and the mechanism of the anaerobic oxidation of the ethanol which is the first step of the steam-iron cycle. To accomplish this, diffuse reflectance spectroscopy (DRIFTS) was used to study the surface composition of the catalysts during the adsorption of ethanol and its transformation during the temperature program. Furthermore, mass spectrometry was used to monitor the desorbed products. The set of studied materials include Cu, Co and Ni ferrites which were also characterized by means of X-ray diffraction, surface area measurements, Raman spectroscopy, and temperature programmed reduction.

In-situ DRIFT/MS study of the conversion of ethanol on mixed Mg/Si oxides

Due to the high price of natural oil and harmful effects of its usage, as the increase in emission of greenhouse gases, the industry focused in searching of sustainable types of the raw materials for production of chemicals. Ethanol, produced by fermentation of sugars, is one of the more interesting renewable materials for chemical manufacturing. There are numerous applications for the conversion of ethanol into commodity chemicals. In particular, the production of 1,3-butadiene whose primary source is ethanol using multifunctional catalysts is attractive. With the 25% of world rubber manufacturers utilizing 1,3-butadiene, there is an exigent need for its sustainable production. In this research, the conversion of ethanol in one-step process to 1,3-butadiene was studied. According to the literature, the mechanisms which were proposed to explain the way ethanol transforms into butadiene require to have both acid and basic sites. But still, there are a lot of debate on this topic. Thus, the aim of this research work is a better understanding of the reaction pathways with all the possible intermediates and products which lead to the formation of butadiene from ethanol. The particular interests represent the catalysts, based on different ratio Mg/Si in comparison to bare magnesia and silica oxides, in order to identify a good combination of acid/basic sites for the adsorption and conversion of ethanol. Usage of spectroscopictechniques are important to extract information that could be helpful for understanding the processes on the molecular level. The diffuse reflectance infrared spectroscopy coupled to mass spectrometry (DRIFT-MS) was used to study the surface composition of the catalysts during the adsorption of ethanol and its transformation during the temperature program. Whereas, mass spectrometry was used to monitor the desorbed products. The set of studied materials include MgO, Mg/Si=0.1, Mg/Si=2, Mg/Si=3, Mg/Si=9 and SiO2 which were also characterized by means of surface area measurements.

Study of Co-based hydrotalcite-derived mixed metal oxides partially modified with silver as potential catalysts for N2O decomposition

Co-Al-Ox mixed metal oxides partially modified with Cu or Mg, as well as Ag were successfully prepared, characterized and evaluated as potential catalysts for the N2O decomposition. The materials were characterized by the following techniques: X-Ray Diffraction, Thermogravimetric Analysis (TGA), N2 Physisorption, Hydrogen Temperature-Programmed Reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS). Ag-modified HT-derived mixed oxides showed enhanced activity compared to the undoped materials, the optimum composition was found for (1 wt.% Ag)CHT-Co3Al. The catalyst characterization studies suggested that the improved catalytic activity of Ag-promoted catalysts were mainly because of the altered redox properties of the materials.

Produzione di idrogeno mediante reforming ciclico dell'etanolo

This work deals with a study on the feasibility of a new process, aimed at the production of hydrogen from water and ethanol (a compound obtained starting from biomasses), with inherent separation of hydrogen from C-containing products. The strategy of the process includes a first step, during which a metal oxide is contacted with ethanol at high temperature; during this step, the metal oxide is reduced and the corresponding metallic form develops. During the second step, the reduced metal compound is contacted at high temperature with water, to produce molecular hydrogen and with formation of the original metal oxide. In overall, the combination of the two steps within the cycle process corresponds to ethanol reforming, where however COx and H2 are produced separately. Various mixed metal oxides were used as electrons and ionic oxygen carriers, all of them being characterized by the spinel (inverse) structure typical of Me ferrites: MeFe2O4 (Me=Co, Ni, Fe or Cu). The first step was investigated in depth; it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation; magnetite was the oxide showing the slower rate of reduction by ethanol, but on the other hand it was that one which could perform the entire cycle of the process more efficiently. Still the problem of coke formation remains the greater challenge to solve.

Reforming dell'etanolo con processo ciclico: studio della reattività di ossidi misti con struttura spinello

This work deals with a study on the feasibility of a new process, aimed at the production of hydrogen from water and ethanol (a compound obtained starting from biomasses), with inherent separation of hydrogen from C-containing products. The strategy of the process includes a first step, during which a metal oxide is contacted with ethanol at high temperature; during this step, the metal oxide is reduced and the corresponding metallic form develops. During the second step, the reduced metal compound is contacted at high temperature with water, to produce molecular hydrogen and with formation of the original metal oxide. In overall, the combination of the two steps within the cycle process corresponds to ethanol reforming, where however COx and H2 are produced separately. Various mixed metal oxides were used as electrons and ionic oxygen carriers, all of them being characterized by the spinel structure typical of M-modified non-stoichiometric ferrites: M0,6Fe2,4O4 (M = Co, Mn or Co/Mn). The first step was investigated in depth; it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation. The new materials were tested in terms of both redox proprieties and catalytic activity to generate hydrogen. Still the problem of coke formation remains the greater challenge to solve.

Studio dell'interazione di etanolo con catalizzatori TiO2-CeOx.

Due to the limited availability of natural oil and the harmful effects of its usage, the industry has focused in searching for sustainable types of raw materials for the production of chemicals. The bioethanol, obtained by fermentation of biomass, has gained particular importance in recent years both as a biofuel, and as a “building block” molecule because it can be considered as a starting reagent to obtain other added value chemical compounds, such as ethylene, acetaldehyde, butadiene and ethyl acetate. The goal of this research was the study of the interaction of ethanol with catalysts based on TiO2-CeOX. Since the electronic properties have implications on the catalytic activity, the idea was to understand if the TiO2-CeOX systems have different reactivity from that of ceria and rutile alone, or an intermediate between them. The study was focused on the characterization of the adsorbed species on the catalysts surface after ethanol adsorption through an in-situ spectroscopic technique (DRIFTS) that allowed us to extract information that could be helpful for the understanding of the processes at the molecular level. The mass spectrometry was used to monitor on-line the desorbed products. Furthermore, reactivity tests in a flow reactor were performed, in order to verify the catalytic behavior of the samples in conditions which are more similar to those applied at an industrial scale. The samples showed to behave in different way depending on the conditions used and the thermal treatment. The particular behavior of the mixed samples with respect to the single oxides is interpreted for each case according to the spectroscopic information collected.