Pre-edge analysis of X-rays absorption spectra in TiO2 modified films

The thesis is mainly focused on the pre-edge analysis of XAS spectra of Ti HCF sample hexacyanocobaltate and hexacyanoferrate samples doped on a Indium Tin Oxide (ITO) thin film. The work is aimed at the determination of Ti oxidation state, as well as indication of various coordination number in the studied samples. The experiment have been conducted using XAFS (X-ray absorption fine structure)beamline at Elettra synchrotron, Trieste (Italy) under supervision of Professor Marco Giorgetti, Department of Industrial Chemistry, University of Bologna. The Master thesis accreditation to fullfill the ASC Master of Advanced Spectroscopy in Chemistry Degree requirement.

Caratterizzazione fisico-chimica di una sorgente di plasma freddo per trattamento di packaging alimentare

I plasmi freddi a pressione atmosferica (CAP) generati da scariche a barriera dielettrica (DBD) sono oggetto di studio e sviluppo per una gamma sempre più ampia di applicazioni in ambito biomedico e industriale come la sanificazione di alimenti e di packaging termosensibili. La sorgente sviluppata in questo progetto di tesi viene definita PASS, Plasma Assisted Sanification System essa è composto da una sorgente di plasma sDBD (surface dielectric barrier discharge), una camera di trattamento, un sistema di raffreddamento e un generatore di alta tensione. Questo progetto si concentra sulla caratterizzazione fisico-chimica di una sorgente di plasma sDBD sviluppata dal gruppo di ricerca in Applicazioni Industriali dei Plasmi (AIP - DIN - Alma Mater Studiorum). In primo luogo è stata svolta una caratterizzazione elettrica della sorgente variando la potenza agendo direttamente sul duty cycle da 100% a 10% tramite due metodi: un metodo convenzionale e con il metodo di Lissajous inserendo una capacità monitor C0 pari a 90,95 nF . Successivamente è stata studiata la cinetica delle concentrazioni di O3 e NO2 in fase gas mediante misure OAS. È stata inoltre monitorata la temperatura all’interno della camera di trattamento per verificare l’ipotesi di assenza di effetti termici durante il trattamento. Un’altra importante applicazione della sorgente di plasma utilizzata in questo è la produzione di acqua attivata al plasma (Plasma Activated Water, PAW). Le specie reattive dell’ossigeno (Reactive Oxygen Species, ROS) e dell’azoto (Reactive Nitrogen Species, RNS), vengono assorbite dal liquido dando origine a ulteriori reazioni chimiche come NO3-, NO2-, H2O2. I RONS influenzano e controllano molti processi nelle piante e sono responsabili del miglioramento della crescita delle piante. Per ogni campione di acqua attivata (PAW) sono stati misurati pH, conducibilità confrontati con la soluzione non trattata e concentrazione di specie reattive quali: H2O2, NO2- e NO3- .

Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.