Flávio F. Ivashita

Nanometric particle size and phase controlled synthesis and characterization of γ-Fe2O3 or (α + γ)-Fe2O3 by a modified sol-gel method

Fe2O3 nanoparticles with sizes ranging from 15 to 53 nm were synthesized by a modified sol-gel method. Maghemite particles as well as particles with admixture of maghemite and hematite were obtained and characterized by XRD, FTIR, UV-Vis photoacoustic and Mossbauer spectroscopy, TEM, and magnetic measurements. The size and hematite/maghemite ratio of the nanoparticles were controlled by changing the Fe:PVA (poly (vinyl alcohol)) monomeric unit ratio used in the medium reaction (1:6, 1:12, 1:18, and 1:24). The average size of the nanoparticles decreases, and the maghemite content increases with increasing PVA amount until 1:18 ratio. The maghemite and hematite nanoparticles showed cubic and hexagonal morphology, respectively. Direct band gap energy were 1.77 and 1.91 eV for A6 and A18 samples. Zero-field-cooling–field-cooling curves show that samples present superparamagnetic behavior. Maghemite-hematite phase transition and hematite Neel transition were observed near 700 K and 1015 K, respectively. Magnet...

Synthesis of goethite in solutions of artificial seawater and amino acids: a prebiotic chemistry study

This study investigated the synthesis of goethite under conditions resembling those of the prebiotic Earth. The artificial seawater used contains all the major elements as well as amino acids (α-Ala, β-Ala, Gly, Cys, AIB) that could be found on the prebiotic Earth. The spectroscopic methods (FT-IR, EPR, Raman), scanning electron microscopy (SEM) and X-ray diffraction showed that in any condition Gly and Cys favoured the formation of goethite, artificial seawater plus β-Ala and distilled water plus AIB favoured the formation of hematite and for the other synthesis a mixture of goethite and hematite were obtained. Thus in general no protein amino acids (β-Ala, AIB) favoured the formation of hematite. As shown by surface enhanced Raman spectroscopy (SERS) spectra the interaction between Cys and Fe 3+ of goethite is very complex, involving decomposition of Cys producing sulphur, as well as interaction of carboxylic group with Fe 3+ . SERS spectra also showed that amino/CN and C-CH 3 groups of α-Ala are interacting with Fe 3+ of goethite. For the other samples the shifting of several bands was observed. However, it was not possible to say which amino acid groups are interacting with Fe 3+ . The pH at point of zero charge of goethites increased with artificial seawater and decreased with amino acids. SEM images showed when only goethite was synthesized the images of the samples were acicular and when only hematite was synthesized the images of the samples were spherical. SEM images for the synthesis of goethite with Cys were spherical crystal aggregates with radiating acicular crystals. The highest resonance line intensities were obtained for the samples where only hematite was obtained. Electron paramagnetic resonance (EPR) and Mossbauer spectra showed for the synthesis of goethite with artificial seawater an isomorphic substitution of iron by seawater cations. Mossbauer spectra also showed that for the synthesis goethite in distilled water plus Gly only goethite was synthesized and in artificial seawater plus Cys a doublet due to interaction of iron with artificial seawater/Cys was observed. It should be pointed out that EPR spectroscopy did not show the interaction of iron with artificial seawater/Cys.

Interaction of forsterite-91 with distilled water and artificial seawater : a prebiotic chemistry experiment

In the present work, the interactions between forsterite-91 with distilled water and forsterite-91 with artificial seawater were studied at two pHs (2.0 and 8.0) using different techniques. A large increase in pH was observed for samples incubated at an initially acidic pH (2.0) due to the dissolution of forsterite-91 in distilled water and artificial seawater. Thus, in acidic hydrothermal vents, an increase in the amount of hydrocarbons and magnetite should be expected due to the release of Fe(II). The pH(PZC) decreased and the pH(IEP) increased when forsterite-91 was treated with distilled water and artificial seawater. The ions from the artificial seawater had an effect on zeta potential. Scanning electron microscopy (SEM) images and X-ray diffractograms showed halite in the samples of forsterite-91 mixed with artificial seawater. The presence of halite or adsorption of ions on the surface of forsterite-91 could affect the synthesis of magnetite and hydrocarbons in hydrothermal vents, due to a decrease in the dissolution rates of forsterite-91. The dissolution of forsterite-91 yields low concentrations of Fe(III) and Mn(II) as detected by electron paramagnetic resonance (EPR) spectroscopy. Microanalysis of forsterite-91 showed a higher amount of Mn, with an oxidation that was likely not + II, as Mn in supernatant solutions was only detected by EPR spectroscopy after mixing with artificial seawater at pH 2.0. As Fe(III) and Mn(II) are catalyst constituents of magnetite and manganese oxide, respectively, their presence is important for synthesis in hydrothermal vents. Etch pits were observed only in the forsterite-91 sample mixed with distilled water at pH 8.0. Na, Cl, S, Ca and K were detected in the samples mixed with artificial seawater by SEM-EDS. Si, Mg, Fe and Al were detected in almost all supernatant samples due to forsterite-91 dissolution. Cr was not dissolved in the experiments, thus Cr in the mineral could serve as an effective catalyst for Fischer Tropsch Types (FTT) reactions in hydrothermal vent systems. X-ray diffractograms of the original forsterite-91 also showed peaks arising from zeolites and clinochlore. After the samples were treated with artificial seawater, X-ray diffractograms showed the dissolution of zeolite. Experiments should be performed in the natural environment to verify the potential for zeolites to act as a catalyst in hydrothermal vents.

The Effects and Role of Polyvinylpyrrolidone on the Size and Phase Composition of Iron Oxide Nanoparticles Prepared by a Modified Sol-Gel Method

Fe2O3 nanoparticles (as maghemite and hematite mixtures) were prepared using adapted sol-gel method from a polyvinylpyrrolidone (PVP) aqueous solution in various Fe3