Materiali ceramici a struttura Aurivillius per la produzione di solar fuels

Solar fuels from CO2 is a topic of current large scientific and industrial interest. In particular, photo-electrochemical cells (PECs) represent today one of the most promising technology for storing sun energy as chemical bonds exploiting carbon dioxide as starting reagent. In this thesis, the possibility of using Aurivillius-type compounds for the production of solar fuels was deeply investigated. Aurivillius-type perovskites, with general formula Bi(n+1)Fe(n-3)Ti3O(3n+3), were synthesized and fully characterized to study the influence of the number of perovskite layers as well as of the synthesis parameters onto their final properties. In particular, 8 different systems were considered increasing the amount of iron and, as a consequence, the number of perovskite layers. These compounds were synthesized through a standard solid-state reaction method as well as via a sol-gel technique and characterized by XRD, SEM and BET analyses. The band gap value and the photocatalytic activity towards Rhodamine B decomposition were assessed as well. For each system, a screen-printing ink was formulated to be deposited as photo-electrodes onto transparent conducting supports. The photo-electrodes were morphologically characterized by XRD and SEM analysis, and their electrochemical properties (cyclic and linear voltammetry, EIS, Mott-Schottky analysis) were determined. Finally, the most promising materials were tested as photo-cathode inside PEC cell under different illumination conditions, to quantify their ability to convert CO2. The obtained results show the potentiality of Aurivillius-type compounds as innovative material for carbon dioxide photo-electrochemical reduction.

Thermal and crystalographic studies of mixture La2O3-SrO prepared via reaction in the solid state

The compound obtained via state solid reaction of the La2O3 and SrO oxides and expose the room atmosphere shows the crystallographic data of the compound reported as La2SrOx. However, thermogravimetric, differential thermal analysis and XRD with controlled temperature indicated that the stoichiometry of the compound is 2La(OH)(3)-SrCO3, which structural parameters were determined by using the Rietveld method. It was verified that when the compound exposed at room atmosphere, the mixture oxide absorbs H2O and CO2 producing hydroxide and carbonate of lanthanum and strontium, respectively, which thermal decomposition occurs by the same steps, producing the La2O3-SrO.

Disposable solid state probe for optical screening of chlorpromazine

We are presenting a simple, low-cost and rapid solid-state optical probe for screening chlorpromazine (CPZ) in aquacultures. The method exploits the colourimetric reaction between CPZ and Fe(III) ion that occurs at a solid/liquid interface, the solid layer consisting of ferric iron entrapped in a layer of plasticized PVC. If solutions containing CPZ are dropped onto such a layer, a colour change occurs from light yellow to dark pink or even light blue, depending on the concentration of CPZ. Visual inspection enables the concentration of CPZ to be estimated. The resulting colouration was also monitored by digital image collection for a more accurate quantification. The three coordinates of the hue, saturation and lightness system were obtained by standard image processing along with mathematical data treatment. The parameters affecting colour were assessed and optimized. Studies were conducted by visible spectrophotometry and digital image acquisition, respectively. The response of the optimized probe towards the concentration of CPZ was tested for several mathematical transformations of the colour coordinates, and a linear relation was found for the sum of hue and luminosity. The limit of detection is 50 μM (corresponding to about 16 μg per mL). The probe enables quick screening for CPZ in real water samples with prior sample treatment.

Preparation and thermal study of Mg-diclofenac compound in solid state

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Thermal Study in Solid State of Zn(II)-Diclofenac Complex: Behavior Kinetic of the Dehydration, Transition Phase and Thermal Decomposition

The dehydration, thermal decomposition and transition phase stage of Zn(II)-diclofenac compound were studied by simultaneous TG-DTA and DSC techniques. The TG and DSC curves of this compound were obtained with the mass of sample of 2 and 5 mg. Additionally, DSC curves were carried out in opened and closed alpha-alumina pans under static and nitrogen atmosphere. The DTA and DSC curves show that this compound possesses exothermic transition phase between 170-180 degrees C, which it is irreversible (monotropic reaction) The kinetics study of this transition phase stage was evaluated by DSC under non-isothermal conditions. The obtained data were evaluated with the isoconversional method, where the values of activation energy (E(a) / kJ mol(-1)) was plotted in function of the conversion degree (alpha). The results show that due to mass sample, different activation energies were obtained From these curves a tendency can be seen where the plots maintain the same profile for closed lids and almost run parallel to each other.

In situ solid state oxidation reaction for La1-xSrxMnO3 (x=0, 0.1, 0.2 and 0.3) formation

In situ solid state oxidation reaction for an alternative La1-xSrxMnO3 (x = 0, 0.1, 0.2 and 0.3) formation is reported. Samples have been obtained by using strontium peroxide, lanthanum and manganese (III) oxide reagents. Strontium peroxide has induced the oxidation of Mn+3 to Mn+4. Lanthanum strontium-doped manganite was obtained without secondary phase formation. La0.825Sr0.175MnO3 showed two structural transitions. The first from 88 to 373 K and the second at 1073 K. which are explained by Jahn-Teller effect at low temperature and cation displacement at high temperature. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Thermal study in solid state of Zn(II)-diclofenac complex: Behavior kinetic of dehydration, transition phase and thermal decomposition

The dehydration, thermal decomposition and transition phase stage of Zn(II)-diclofenac compoundwere studied by simultaneous TG-DTA and DSC techniques. The TG and DSC curves of this compoundwere obtained with the mass of sample of 2 and 5 mg. Additionally, DSC curves were carried out inopened and closed a-alumina pans under static and nitrogen atmosphere. The DTA and DSC curves showthat this compound possesses exothermic transition phase between 170-180 ºC, which it is irreversible(monotropic reaction). The kinetics study of this transition phase stage was evaluated by DSC undernon-isothermal conditions. The obtained data were evaluated with the isoconversional method, where thevalues of activation energy (Ea/kJmol-1) was plotted in function of the conversion degree (a). The resultsshow that due to mass sample, different activation energies were obtained. From these curves a tendencycan be seen where the plots maintain the same profile for closed lids and almost run parallel to each other.

Reaction pathways in the solid state synthesis of multiferroic BiFeO 3

The obtaining of multiferroicBiFeO3 as a pure single-phase product is particularly complex since the formation of secondary phases seems to be unavoidable. The process by which these secondary impurities are formed is studied by analyzing the diffusion and solidstate reactivity of the Bi2O3–Fe2O3 system. Experimental evidence is reported which indicates that the progressive diffusion of Bi3+ ions into the Fe2O3 particles governs the solidstatesynthesis of the perovskite BiFeO3 phase. However a competition is established between the diffusion process which tends to complete the formation of BiFeO3, and the crystallization of stable Bi2Fe4O9 mullite crystals, which tend to block that formation reaction.

Reaction pathways in the solid state synthesis of multiferroic BiFeO3

The obtaining of multiferroic BiFeO3 as a pure single-phase product is particularly complex since the formation of secondary phases seems to be unavoidable. The process by which these secondary impurities are formed is studied by analyzing the diffusion and solid state reactivity of the Bi2O3?Fe2O3 system. Experimental evidence is reported which indicates that the progressive diffusion of Bi3+ ions into the Fe2O3 particles governs the solid state synthesis of the perovskite BiFeO3 phase. However a competition is established between the diffusion process which tends to complete the formation of BiFeO3, and the crystallization of stable Bi2Fe4O9 mullite crystals, which tend to block that formation reaction.

Photochemically induced nuclear spin polarization in reaction centers of photosystem II observed by 13C-solid-state NMR reveals a strongly asymmetric electronic structure of the P680.+ primary donor chlorophyll

We report 13C magic angle spinning NMR observation of photochemically induced dynamic nuclear spin polarization (photo- CIDNP) in the reaction center (RC) of photosystem II (PS2). The light-enhanced NMR signals of the natural abundance 13C provide information on the electronic structure of the primary electron donor P680 (chlorophyll a molecules absorbing around 680 nm) and on the pz spin density pattern in its oxidized form, P680⨥. Most centerband signals can be attributed to a single chlorophyll a (Chl a) cofactor that has little interaction with other pigments. The chemical shift anisotropy of the most intense signals is characteristic for aromatic carbon atoms. The data reveal a pronounced asymmetry of the electronic spin density distribution within the P680⨥. PS2 shows only a single broad and intense emissive signal, which is assigned to both the C-10 and C-15 methine carbon atoms. The spin density appears shifted toward ring III. This shift is remarkable, because, for monomeric Chl a radical cations in solution, the region of highest spin density is around ring II. It leads to a first hypothesis as to how the planet can provide itself with the chemical potential to split water and generate an oxygen atmosphere using the Chl a macroaromatic cycle. A local electrostatic field close to ring III can polarize the electronic charge and associated spin density and increase the redox potential of P680 by stabilizing the highest occupied molecular orbital, without a major change of color. This field could be produced, e.g., by protonation of the keto group of ring V. Finally, the radical cation electronic structure in PS2 is different from that in the bacterial RC, which shows at least four emissive centerbands, indicating a symmetric spin density distribution over the entire bacteriochlorophyll macrocycle.

Natural abundance solid-state carbon NMR studies of photosynthetic reaction centers with photoinduced polarization.

Solid-state NMR spectra of natural abundance 13C in reaction centers from photosynthetic bacteria Rhodobacter sphaeroides R-26 was measured. When the quinone acceptors were removed and continuous visible illumination of the sample was provided, exceptionally strong nuclear spin polarization was observed in NMR lines with chemical shifts resembling those of the aromatic carbons in bacteriochlorophyll and bacteriopheophytin. The observation of spin polarized 15N nuclei in bacteriochlorophyll and bacteriopheophytin was previously demonstrated with nonspecifically 15N-labeled reaction centers. Both the carbon and the nitrogen NMR studies indicate that the polarization is developed on species that carry unpaired electrons in the early electron transfer steps, including the bacteriochlorophyll dimer donor P860 and probably the bacteriopheophytin acceptor. I. Both enhanced-absorptive and emissive polarization were seen in the carbon spectrum; most lines were absorptive but the methine carbons of the porphyrin ring (alpha, beta, gamma, ) exhibited emissive polarization. The change in the sign of the hyperfine coupling at these sites indicates the existence of nodes in the spin density distribution on the tetrapyrrole cofactors flanking each methine carbon bridge.

Numerical method for determination of the NMR frequency of the single-qubit operation in a silicon-based solid-state quantum computer

A numerical method is introduced to determine the nuclear magnetic resonance frequency of a donor (P-31) doped inside a silicon substrate under the influence of an applied electric field. This phosphorus donor has been suggested for operation as a qubit for the realization of a solid-state scalable quantum computer. The operation of the qubit is achieved by a combination of the rotation of the phosphorus nuclear spin through a globally applied magnetic field and the selection of the phosphorus nucleus through a locally applied electric field. To realize the selection function, it is required to know the relationship between the applied electric field and the change of the nuclear magnetic resonance frequency of phosphorus. In this study, based on the wave functions obtained by the effective-mass theory, we introduce an empirical correction factor to the wave functions at the donor nucleus. Using the corrected wave functions, we formulate a first-order perturbation theory for the perturbed system under the influence of an electric field. In order to calculate the potential distributions inside the silicon and the silicon dioxide layers due to the applied electric field, we use the multilayered Green's functions and solve an integral equation by the moment method. This enables us to consider more realistic, arbitrary shape, and three-dimensional qubit structures. With the calculation of the potential distributions, we have investigated the effects of the thicknesses of silicon and silicon dioxide layers, the relative position of the donor, and the applied electric field on the nuclear magnetic resonance frequency of the donor.

Quantitative analysis of solid-state processes studied with isothermal microcalorimetry

Quantitative analysis of solid-state processes from isothermal microcalorimetric data is straightforward if data for the total process have been recorded and problematic (in the more likely case) when they have not. Data are usually plotted as a function of fraction reacted (α); for calorimetric data, this requires knowledge of the total heat change (Q) upon completion of the process. Determination of Q is difficult in cases where the process is fast (initial data missing) or slow (final data missing). Here we introduce several mathematical methods that allow the direct calculation of Q by selection of data points when only partial data are present, based on analysis with the Pérez-Maqueda model. All methods in addition allow direct determination of the reaction mechanism descriptors m and n and from this the rate constant, k. The validity of the methods is tested with the use of simulated calorimetric data, and we introduce a graphical method for generating solid-state power-time data. The methods are then applied to the crystallization of indomethacin from a glass. All methods correctly recovered the total reaction enthalpy (16.6 J) and suggested that the crystallization followed an Avrami model. The rate constants for crystallization were determined to be 3.98 × 10-6, 4.13 × 10-6, and 3.98 × 10 -6 s-1 with methods 1, 2, and 3, respectively. © 2010 American Chemical Society.

Organometallic derivatives of cyclotriphosphazene as precursors of nanostructured metallic materials: a new solid state method

The cyclic phosphazene trimers [N3P3(OC6H5)5OC5H4N·Ti(Cp)2Cl][PF6] (3), [N3P3(OC6H4CH2CN·Ti(Cp)2Cl)6][PF6]6 (4), [N3P3(OC6H4-But)5(OC6H4CH2CN·Ti(Cp)2Cl)][PF6] (5), [N3P3(OC6H5)5C6H4CH2CN·Ru(Cp)(PPh3)2][PF6] (6), [N3P3(OC6H5)5C6H4CH2CN·Fe(Cp)(dppe)][PF6] (7) and N3P3(OC6H5)5OC5H4N·W(CO)5 (8) were prepared and characterized. As a model, the simple compounds [HOC5H5N·Ti(Cp)2Cl]PF6 (1) and [HOC6H4CH2CN·Ti(Cp)2Cl]PF6 (2) were also prepared and characterized. Pyrolysis of the organometallic cyclic trimers in air yields metallic nanostructured materials, which according to transmission and scanning electron microscopy (TEM/SEM), energy-dispersive X-ray microanalysis (EDX), and IR data, can be formulated as either a metal oxide, metal pyrophosphate or a mixture in some cases, depending on the nature and quantity of the metal, characteristics of the organic spacer and the auxiliary substituent attached to the phosphorus cycle. Atomic force microscopy (AFM) data indicate the formation of small island and striate nanostructures. A plausible formation mechanism which involves the formation of a cyclomatrix is proposed, and the pyrolysis of the organometallic cyclic phosphazene polymer as a new and general method for obtaining metallic nanostructured materials is discussed.