The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro‐spectroscopy and electrochemical polarisation. Part I: near‐resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds

Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5‐nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near‐resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α‐Fe₂O₃), maghemite (γ‐Fe₂O₃), magnetite (Fe₃O₄), goethite (α‐FeOOH), akaganeite (β‐FeOOH), lepidocrocite (γ‐FeOOH) and feroxyhyte (δ‐FeOOH). Optimum enhancement, when compared to that with the 514.5‐nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm⁻¹) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of copiapites Fe2+Fe3+(SO4)6(OH)2 · 20H2O: environmental implications

Raman spectroscopy has been used to study selected mineral samples of the copiapite group. Copiapite (Fe²⁺Fe³⁺(SO₄)₆(OH)₂ · 20H₂O) is a secondary mineral formed through the oxidation of pyrite. Minerals of the copiapite group have the general formula AFe₄(SO₄)₆(OH)₂ · 20H₂O, where A has a + 2 charge and can be either magnesium, iron, copper, calcium and/or zinc. The formula can also be B_2/3Fe₄(SO₄)₆(OH)₂ · 20H₂O, where B has a + 3 charge and may be either aluminium or iron. For each mineral, two Raman bands are observed at around 992 and 1029 cm⁻¹, assigned to the (SO₄)²⁻ν₁ symmetric stretching mode. The observation of two bands provides evidence for the existence of two non‐equivalent sulfate anions in the mineral structure. Three Raman bands at 1112, 1142 and 1161 cm⁻¹ are observed in the Raman spectrum of copiapites, indicating a reduction of symmetry of the sulfate anion in the copiapite structure. This reduction in symmetry is supported by multiple bands in the ν₂ and ν₄(SO₄)²⁻ spectral regions. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of multi–wall carbon nanotubes supported-hydrated iron phosphate cathode material for lithium–ion cells by a novel homogeneous precipitation method

Iron phosphate (FePO₄) is a promising candidate for the cathode material in lithium-ion cells due to its easy synthesis and low cost. However, the intrinsic drawbacks of FePO₄ material (i.e., the low electronic conductivity and the low lithium-ion diffusion coefficient) result in poor capacity. To overcome the shortcomings, multi-wall carbon nanotubes (MWNTs) supported hydrated iron phosphate nanocomposites (FePO₄·2H₂O/MWNTs) are prepared using a novel homogeneous precipitation method. Meanwhile, the formation mechanism of highly dispersed and ultrafine FePO₄·2H₂O nanoparticles is discussed in detail. Electrochemical measurements show that FePO₄·2H₂O/MWNTs nanocomposites have a superior discharge capacity and stability. For example, FePO₄·2H₂O/MWNTs nanocomposites exhibit a high initial discharge capacity (129.9?mAhg^?1) and a stable capacity retention (114.3?mAhg^?1 after 20 cycles). The excellent electrochemical performance is attributed to the small particle size of FePO₄·2H₂O nanoparticles, the good electronic conductivity of MWNTs, and the three-dimensional conductive network structure of FePO₄·2H₂O/MWNTs nanocomposites.     

Mössbauer structural investigation of Fe2O3−TiO2 gels

Fe₂O₃?TiO₂ powders were obtained by the sol-gel method through hydrolysis and polycondensation of titanium n-butoxide and different iron compounds in alcoholic solutions. As iron oxide precursors, Fe(III)ethoxide, Fe(III)acetylacetonate and Fe(NO₃)₃·9H₂O were employed. The gels were dried and heat treated in air and in nitrogen atmosphere at different temperatures. It was demonstrated by means of Mössbauer spectroscopy that the use of different iron precursors can slightly affect the oxidation state of iron and the nature of the crystalline phases developed only when the heat treatment is performed in a non-oxidizing atmosphere. The results are discussed also in connection with previous X-ray diffraction data.     

Effect of the Calcination Atmosphere on the Structural Properties of the Reduced Fe/SiO2 System

Iron supported systems are frequently used as catalysts in the Fischer–Tropsch synthesis being the Fe⁰ the active phase for the reaction. We have studied the influence of the calcination atmosphere (air or nitrogen) on the iron oxide reducibility and the metallic iron particle size obtained in Fe/SiO₂ system. We have impregnated a silicagel with Fe(NO₃)₃·9H₂O aqueous solution and the solid obtained was calcinated in air or N₂ stream. These precursors, with 5% (wt/wt) of Fe, were characterized by Mössbauer Spectroscopy at 298 and 15 K. Amorphous Fe₂O₃ species with 3 nm diameter in the former, and α-Fe₂O₃ crystals of 48 nm diameter were detected in the last one. Both precursors were reduced in H₂ stream. Two catalysts were obtained and characterized by Mössbauer spectroscopy in controlled atmosphere at 298 and 15 K, CO chemisorption and volumetric oxidation. α-Fe⁰, Fe₃O₄ and Fe²⁺ were identified in the catalyst calcined in air. Instead, only α-Fe⁰ was detected in the catalyst calcined in N₂. The iron metallic crystal sizes were estimated as ≈2 nm for the former and ≈29 nm for the last one. The different oxide crystal sizes, obtained from the diverse calcination atmospheres, have led to different structural properties of the reduced solids. It has been possible to reduce totally the existing iron in an Fe/SiO₂ system with iron loading lower than 10% (wt/wt).     

Mechanism of solid-state oxidation of FeSO4·H2O: model of simultaneous reactions

The mechanism of the thermal transformation of FeSO₄·H₂O in air has been studied under isothermal conditions at temperatures (150–460)°C using mainly⁵⁷Fe Mössbauer spectroscopy and X-ray powder diffraction (XRD). Two trends are typical for the thermal behaviour of FeSO₄·H₂O in air, a tendency toward oxidation and dehydration. We suggested a new transformation model consisting of two ways of oxidation, direct one and indirect one. Fe(OH)SO₄ was identified as a product of the direct way, Fe₂(SO₄)₃ and superparamagnetic nanoparticles ofγ-Fe₂O₃ as products of the indirect way. The suggested model of simultaneous reactions explains the unusual non-monotonous dependence of the oxidation level of the thermally treated samples on temperature.     

Infrared and Raman spectra of aquamolybdenum (VI) oxide hydrate (MoO3·2H2O)

The infrared and Raman spectra of MoO₃·2H₂O are recorded and analysed on the basis of vibrations due to MoO₆ octahedra and H₂O molecules. Considerable changes in the frequencies of the octahedra have been observed due to strong distortion in the octahedral arrangement. The inactivev ₆ vibration of O _h symmetry became active in the Raman spectrum. Co-ordinated (aquated) and hydrated (interlayer) water molecules give rise to different frequencies.     

Preparation of PtSnRh/C-Sb2O5·SnO2 electrocatalysts by an alcohol reduction process for direct ethanol fuel cell

PtSnRh/C-Sb₂O₅·SnO₂ electrocatalysts with different Pt/Sn/Rh atomic ratios (90:05:05, 70:25:05, and 50:45:05) were prepared by an alcohol reduction process using H₂PtCl₆·6H₂O, SnCl₂·2H₂O, RhCl₃·xH₂O as metal sources, ethylene glycol as solvent and reducing agent, and a physical mixture of Vulcan XC72 (85?wt%) and Sb₂O₅·SnO₂ (15?wt%) as support. The electrocatalysts were characterized by X-ray diffraction and transmission electron microscopy. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at 25 and 50?°C and in single direct ethanol fuel cell (DEFC) at 100?°C. The diffractograms of PtSnRh/C-Sb₂O₅·SnO₂ electrocatalysts showed the peaks characteristic of Pt face-centered cubic structure and several others peaks associated with ·SnO₂ and Sb₂O₅·SnO₂. Transmission electron micrographs of PtSnRh/C-Sb₂O₅·SnO₂ electrocatalysts showed the metal nanoparticles distributed on the supports with particle sizes of about 2?C3?nm. The electrochemical measurements and the experiments in a single DEFC showed that PtSnRh/C-Sb₂O₅·SnO₂ (90:05:05) and PtSnRh/C-Sb₂O₅·SnO₂ (70:25:05) electrocatalysts exhibited higher performance for ethanol oxidation in comparison with PtSnRh/C electrocatalyst.     

Phase transformations in CaCO3/iron oxide composite induced by thermal treatment and laser irradiation

Calcium carbonate (CaCO₃)/iron oxide composites were synthesized through a simple one‐step impregnation procedure by mixing iron oxide nanoparticles (γ‐Fe₂O₃ and Fe₃O₄) of about 6 nm in size and CaCO₃ microparticles (Φ = 2 µm–8 µm, vaterite phase). The morphology and structural properties of CaCO₃, iron oxide nanoparticles and CaCO₃/iron oxide composites were characterized as a function of low iron content (0 %w to 3.2 %w) by scanning electron microscopy and transmission electron microscopy, X‐ray diffraction and ⁵⁷Fe Mössbauer spectrometry. The phase transformations induced by thermal treatment and laser irradiation were investigated in situ by X‐ray thermodiffraction (XRTD) and Raman spectroscopy. We have shown that the phase transformations observed by XRTD are also observed under laser irradiation as a consequence of the absorption of the laser irradiation by iron oxide nanoparticles. Copyright © 2012 John Wiley & Sons, Ltd.     

Phonons and electronic transitions in the Raman spectra of FeCl2·2H2O and isomorphic compounds

The Raman spectra in FeCl₂ · 2H₂O (FC2) and the isomorphic compounds FeCl₂ · 2D₂O (FC2D), MnCl₂ · 2H₂O (MC2) and CoCl₂ · 2H₂O (CC2) were observed at 2 K to obtain the frequencies of all 12 optical phonons of even symmetry at the zone center. The lowest of these phonons is known to be coupled resonantly to the magnons below T_N. This coupling and other important magnetic properties of the iron salts are determined by the influence of the crystal field. The electronic transitions of the Fe²⁺-ion in a crystal field are identified after a thorough assignment of the phonon lines in the four isomorphic compounds to symmetry types, using back-scattering and 90°-scattering techniques.     

Analysis of atmospheric corrosion products of steel and coated steel by means of scattering Mössbauer spectrometry

Wearthering steels treated with and without zinc phosphate solution were exposed to atmosphere for 15 years and rust layers produced on the steels were analysed by scattering Mössbauer spectrometry (CEMS and XMS). γ-FeOOH, fine α-FeOOH, 5Fe₂O₃·9H₂O, γ-Fe₂O₃ and Fe₃O₄ were identified to be present in the rust formed on the steel without phosphate coating. Large particles of γ-Fe₂O₃ and Fe₃O₄ formed on the uncoated steel exposed to atmosphere in a position facing north on vertical plane. The layer structure of rust was affected by the position. The thin rust layer formed on the phosphate + carylite resin coated steel was considered to consist of γ-FeOOH, fine α-FeOOH, and fine γ-Fe₂O₃.     

Synthesis of carbon-coated Fe3O4 nanorods as electrode material for supercapacitor

Carbon-coated Fe₃O₄ and pure Fe₃O₄ nanorods are synthesized via hydrothermal reaction and subsequent sintering procedure. The as-prepared products characterized by X-ray diffraction and scanning electron microscopy analysis indicate that carbon coating does not affect the structure and morphology of Fe₃O₄. Transmission electron microscope shows that Fe₃O₄ nanorods are homogeneously coated by carbon layer with a thickness of approximately 2 nm. The electrochemical properties measured by cyclic voltammetry, galvanostatic charge–discharge cycling and electrochemical impedance spectroscopy tests show that carbon-coated Fe₃O₄ (Fe₃O₄/C) nanorods present improved electrochemical performance due to the carbon layer. A specific capacitance of 275.9 F?g^?1 is achieved at a current density of 0.5 A g^?1 in 1 M Na₂SO₃ aqueous solution for the Fe₃O₄/C nanorods in comparison to that of 208.6 F?g^?1 for pure Fe₃O₄.     

Protonic conductivity and lithium intercalation in a new iron hydroxyphosphate hydrate: (H3O)[Fe(H2O)]3[H8(PO4)6]·3H2O

A new hydroxonium iron phosphate, (H₃O)[Fe(H₂O)]₃[H₈(PO₄)₆]·3H₂O, was synthesized through a precipitation route by means of acidic media. The crystal structure was solved by X-ray powder diffraction. Electrochemical characterizations, performed on this compound, show reversible intercalation of lithium and substantial lithium diffusion. Protonic conductivity is observed in agreement with the simultaneous presence of H₂O, hydrated protons and OH groups in the large intersecting tunnels of this intersecting tunnel structure.     

Mössbauer study of a Fe3O4/PMMA nanocomposite synthesized by sonochemistry

Magnetite nanoparticles of 10 nm average size were synthesized by ultrasonic waves from the chemical reaction and precipitation of ferrous and ferric iron chloride (FeCl₃ · 6H₂O y FeCl₂ · 4H₂O) in a basic medium. The formation and the incorporation of the magnetite in PMMA were followed by XRD and Mössbauer Spectroscopy. These magnetite nanoparticles were subsequently incorporated into the polymer by ultrasonic waves in order to obtain the final sample of 5 % weight Fe₃O₄ into the polymethylmethacrylate (PMMA). Both samples Fe₃O₄ nanoparticles and 5 % Fe₃O₄/PMMA nanocomposite, were studied by Mössbauer spectroscopy in the temperature range of 300 K–77 K. In the case of room temperature, the Mössbauer spectrum of the Fe₃O₄ nanoparticles sample was fitted with two magnetic histograms, one corresponding to the tetrahedral sites (Fe^3?+?) and the other to the octahedral sites (Fe^3?+? and Fe^2?+?), while the 5 % Fe₃O₄/PMMA sample was fitted with two histograms as before and a singlet subspectrum related to a superparamagnetic behavior, caused by the dispersion of the nanoparticles into the polymer. The 77 K Mössabuer spectra for both samples were fitted with five magnetic subspectra similar to the bulk magnetite and for the 5 % Fe₃O₄/PMMA sample it was needed to add also a superparamagnetic singlet. Additionally, a study of the Verwey transition has been done and it was observed a different behavior compared with that of bulk magnetite.     

Raman spectroscopic study of synthetic reevesite and cobalt substituted reevesite (Ni,Co)6Fe2(OH)16(CO3)·4H2O

Raman spectroscopy, complemented with infrared spectroscopy of compounds equivalent to reevesite, formula (Ni,Co)₆Fe₂(OH)₁₆(CO₃)·4H₂O, with the ratio of Ni/Co ranging from 0 to 1, have been synthesised and characterised based on the molecular structure of the synthesised mineral. The combination of Raman spectroscopy with infrared spectroscopy enables an assessment of bands attributable to water stretching and brucite‐like surface hydroxyl units to be obtained. Raman spectroscopy shows a reduction in the symmetry of the carbonate anion, leading to the conclusion that the carbonate anion is bonded to the brucite‐like hydroxyl surface and to the water in the interlayer. Variation in the position of the carbonate anion stretching vibrations occurs and is dependent on the Ni/Co ratio. Water bending modes are identified in both the Raman and infrared spectra at positions greater than 1620 cm⁻¹, indicating that water is strongly hydrogen bonded to both the interlayer anions and the hydrotalcite surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Assessment of role of iron ions on the physical and spectroscopic properties of multi-component Na2O−PbO−Bi2O3−SiO2 glass ceramics

Multi-component glass ceramics composition Na₂O?PbO?Bi₂O₃?SiO₂ doped with different concentrations of Fe₂O₃ as nucleating agent were characterised by XRD, SEM (scanning electron microscope) and DTA (differential thermal analysis) techniques. Optical absorption, EPR, FTIR and Raman studies are also carried out on these glass ceramics. Absorption bands observed at about 457, 489, 678 and 820 nm are the characteristics of Fe³⁺ ions whereas the band observed at about 964 nm is due to Fe²⁺ ions. EPR studies suggested that Fe³⁺ ions entered in the lattice as tetragonally distorted octahedral symmetry or rhombic sites at low concentration of Fe₂O₃, whereas at higher concentration of Fe₂O₃ (beyond 1 mol%), the super exchange type of interactions between multivalency iron ions begin to dominate. FTIR and Raman spectra have revealed the behaviour of various structural units in the glass ceramic matrix. The analysis of these spectroscopic studies indicates that iron ions do exist in Fe³⁺ and Fe²⁺ state.     

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

The potential for using hydroxyl radical (OH^?) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H₂O₂ addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H₂O₂ by NP surface generated OH^? were investigated. Depending on the ratio of iron and H₂O₂, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.     

Electrocatalytic activity of a Gd2Ti0.6Mo1.2Sc0.2O7-δ anode towards hydrogen and methane electro-oxidation in a solid oxide fuel cell

Mixed conducting oxide anodes are being considered for the direct utilisation of natural gas in high temperature fuel cells. This work refers to the electrochemical characterization of the pyrochlore Gd₂Ti_0.6Mo_1.2Sc_0.2O_7-δ (GTMS) as anode in a solid oxide fuel cell running in low humidity hydrogen or methane. The electro-oxidation reaction was investigated using impedance spectroscopy, potentiostatic measurements and cyclic voltammetry. Kinetic data were obtained for different fuels in the temperature range 845–932 °C. In a methane-fuelled cell, steam reforming appears to be the rate-limiting step. The overall polarisation resistance of the anode under open circuit conditions at 932 °C was 6.86 Ω·cm² in 97% H₂/3% H₂O, and 43 Ω·cm² in 97% CH₄/3% H₂O. For a 97% fuel-3% H₂O/GTMS//YSZ-Al₂O₃//Pt/air cell, the maximum power output at 932 °C was 9.5 mW/cm² and 1.8 mW/cm² in hydrogen and methane, respectively. First investigations on this type of electrode material show unidentified peaks on XRD spectra after electrochemical test, which indicate GTMS instability under experimental conditions. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Electrochemical characterisation of the Pt/YSZ interface exposed to a reactive gas phase

The Pt/yttria-stabilized cubic zirconia (YSZ) interface exposed to a reactive gas was characterised by solid electrolyte potentiometry and cyclic voltammetry. The catalytic reactions included total combustion of C₃H₈ and C₃H₆ to CO₂ and H₂O as well as NO reduction by C₃H₆ in the presence of O₂ under oxygen-rich and stoichiometric conditions. The solid electrolyte potentiometry as a function of the temperature in C₃H_x/O₂ (with x=6 or 8) reflected the catalytic properties of Pt for C₃H_x oxidation. In C₃H₆/NO/O₂, the reduction of NO was evidenced below 300 °C. The cyclic voltammetry evidenced the formation of an oxygen chemisorbed layer on the Pt surface under anodic potential. Propane had no effect on this chemisorbed layer, whereas propene weakened significantly the strength of this Pt–O bond. Addition of NO to C₃H₆/O₂ led to the disappearing of this chemisorbed layer. The use of solid electrolyte potentiometry in conjunction with cyclic voltammetry allowed us to determine the surface oxidation state of Pt during the catalytic reactions.