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).     

Effect of Sn on methane decomposition over Fe supported catalysts to produce carbon

In this work, alumina-supported Sn containing Fe catalysts were investigated in CVD reactions (Chemical Vapor Deposition) using methane for carbon production. The catalysts were prepared with 10 wt.% of Fe (as Fe₂O₃) and 3, 6 and 12 wt.% of Sn (as SnO₂) supported on Al₂O₃ named hereon Fe10Sn3A, Fe5Sn6A and Fe10Sn12A, respectively. These catalysts were characterized by SEM, TPCVD, TPR, TG, Raman, XRD and ⁵⁷Fe and ¹¹⁹Sn Mössbauer spectroscopy. Methane reacts with Fe10A catalyst (without Sn) in the temperature range 680?C900°C to produce mainly Fe⁰, Fe₃C and 20 wt.% of carbon deposition. TPR and TPCVD clearly showed that Sn strongly hinders the CH₄ reaction over Fe catalyst. ⁵⁷Fe Mössbauer suggested that in the presence of Sn the reduction of Fe^?+?3 by methane becomes very difficult. ¹¹⁹Sn Mössbauer showed Sn^?+?4 species strongly interact with metallic iron after CVD, producing iron-tin phases such as Fe₃SnC and FeSn₂. This interaction Sn?CFe increases the CVD temperatures and decreases the carbon yield leading to the production of more organized forms of carbon such as carbon nanotubes, nanofibers and graphite.     

Fe-ZSM-5杂原子分子筛的合成与表征

采用静态水热法分别以正丁胺、四丙基溴化铵为模板剂合成ZSM-5分子筛及Fe-ZSM-5杂原子分子筛；利用XRD与FT-IR对其结构进行表征；考察了Mo改性后分子筛催化剂上甲烷脱氢芳构化的反应性能。结果表明，Fe部分进入了分子筛的骨架，导致分子筛的结晶度及表面酸强度的下降，使Mo／Fe-ZSM-5催化剂的反应性能较Mo／HZSM-5显著下降。     

Mössbauer effect phase determination in iron oxide–polyaniline nanocomposites

Mössbauer effect spectroscopy and thermal analysis techniques were applied to characterize polyaniline composites successfully synthesized by embedding Fe oxide nanoparticles (about 10–13 nm) in a polymeric matrix in the presence of dodecyl benzene sulfonic acid and HCl (dopant). Thermal techniques provided quantitative information on iron oxide content and on polyaniline stability and transformations. Mössbauer results indicated that for the whole studied composition range, 3.4 to 100 iron oxide wt.%, composites hold maghemite particles. A preliminary study of the conductivity of the nanocomposites was performed. The largest conductivity was observed for a 8 wt.% maghemite composite where all particles are magnetically unblocked at room temperature within the Mössbauer time window.     

Investigations of redistribution of iron in a zirconium alloy due to neutron irradiation

Data were obtained with the help of ⁵⁷Fe Mössbauer spectroscopy about the redistribution of iron atoms between intermetallic precipitates and between precipitates and the solid solution phase in E635-type alloy (Zr-1.2 wt% Sn-0.34 wt% Fe-1.0 wt %Nb-0.03–0.05 wt% O) due to neutron irradiation.     

Mössbauer spectroscopic studies of Fe-20 wt.% Cr ball milled alloy

Interesting differences were noticed in the alloying process during ball milling of Fe-10 wt.% Cr and Fe-20 wt.% Cr alloys by ⁵⁷Fe Mössbauer spectroscopic studies. In both cases, there is almost no diffusion of Fe in Cr or vice versa up to 20 h of milling time. As the powders are milled for another 20 h substantive changes occur in the Mössbauer spectra showing atomic level mixing. But the two compositions behave differently with respect to alloying. Fe-20 wt.% Cr sample does not differ much in the hyperfine field distribution as it is milled from 40 to 100 h. On the other hand, the hyperfine field distribution keeps on changing with milling time for Fe-10 wt.% Cr sample even up to 100 h of milling. The average crystallite size is found to be 7.5 nm for Fe-10 wt.% Cr and 6.5 nm in Fe-20 wt.% Cr after milling.     

Thermodynamic analysis of nanoparticle size effect on kinetics in Fischer–Tropsch synthesis by lanthanum promoted iron catalyst

The kinetic parameters of the Fischer–Tropsch synthesis (FTS) on iron catalyst are analyzed by size-dependent thermodynamic method. A Langmuir–Hinshelwood kinetic equation is considered for evaluation of catalytic activity of lanthanum promoted iron catalyst. A series of unsupported iron catalysts with different particle sizes were prepared via microemulsion method. The experimental results showed that catalyst activity pass from a maximum value by increasing the iron particle size. Also, data presented that iron particle size has considerable effects on adsorption parameters and FTS rates. The ratio of surface tension (σ) to nanoparticle radius (r) is important in FTS reaction on iron catalyst. Finally, the results showed that by increasing of iron particle size from 18 to 45 nm the activation energies of catalysts and heats of adsorption of catalysts as two main parameters of FTS reaction increased from 89 to 114 kJ/mol and from 51 to 71 kJ/mol, respectively.     

Aggregates of iron in ytterbium films

Films of ytterbium doped with iron (0.3?C1.6 at.% Fe) have been prepared by co-deposition of atomic beams of the elements onto Kapton substrates under high vacuum. Iron is immiscible in ytterbium and various iron species are expected to occur. XRD reveals a mixture of fcc and hcp ytterbium. The Mössbauer spectra are interpreted with contributions from monomeric iron on interstitial sites, two types of neighboring substitutional iron aggregates and two types of clusters formed upon diffusion. The present data supplement earlier data obtained for 0.5 and 5 at.% Fe. There is no systematic correlation of cluster formation with increasing iron concentration. There are indications that clusters are formed more easily for thin films. We conclude that cluster formation occurs mainly on the film surface and is limited by the slow diffusion from inside films.     

Electrochemical water splitting using nano-zeolite Y supported tungsten oxide electrocatalysts

Zeolites are often used as supports for metals and metal oxides because of their well-defined microporous structure and high surface area. In this study, nano-zeolite Y (50–150 nm range) and micro-zeolite Y (500–800 nm range) were loaded with WO₃, by impregnating the zeolite support with ammonium metatungstate and thermally decomposing the salt thereafter. Two different loadings of WO₃ were studied, 3 wt.% and 5 wt.% with respect to the overall catalyst. The prepared catalysts were characterized for their morphology, structure, and surface areas through scanning electron microscope (SEM), XRD, and BET. They were further compared for their electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H₂SO₄. On comparing the bare micro-zeolite particles with the nano-form, the nano-zeolite Y showed higher currents with comparable overpotentials and lower Tafel slope of 62.36 mV/dec. WO₃ loading brought about a change in the electrocatalytic properties of the catalyst. The overpotentials and Tafel slopes were observed to decrease with zeolite-3 wt.% WO₃. The smallest overpotential of 60 mV and Tafel slope of 31.9 mV/dec was registered for nano-zeolite with 3 wt.% WO₃, while the micro-zeolite gave an overpotential of 370 mV and a Tafel slope of 98.1 mV/dec. It was concluded that even with the same metal oxide loading, nano-zeolite showed superior performance, which is attributed to its size and hence easier escape of hydrogen bubbles from the catalyst.     

From Ore to Tool – Iron Age Iron Smelting in the Largest and Oldest Meteorite Crater in the World

The Vredefort Impact Structure in South Africa is the biggest and oldest remnant meteorite impact crater in the world where various ancient cultures thrived. In this paper some light will be shed on the Iron Age, iron smelting aspects of the people that inhabited the area and the results of a laboratory study of iron artefacts and a possible source of iron ore in the region is given. A sectional piece from a hoe manufactured in a small bloomery furnace was polished and etched and subsequently analyses with SEM and Mössbauer techniques were obtained. The hoe has a typical cast iron composition (2.9% C, 0.1% Mn, 0.4% Si, 0.4% P and 96.2% Fe, all wt.%) and contains many slag inclusions with wustite dendrites. The Mössbauer spectrum consisted of iron (86%), wustite (5%) and oxihydroxide (9%) and the thin (200 μm) corrosion layer consisted of hematite (55%) and oxihydroxides (45%). At a furnace site, various slag clumps (26.3% C, 24.8% SiO₂, 11.3% Al₂O₃, 1.3% P₂O₅, 1.0% K₂O, 0.4% CaO and 30.2 FeO, all wt.%, average of four samples) and iron nodules (7.6% C, 6.0% Mn, 4.3% Si, 1.4% Al, 80.7% Fe, all wt.%) were found. The Mössbauer spectrum of the slag consisted of iron (7%), magnetite (56%), fayalite (2%) and oxihydroxides (35%) and that of the iron nodules yielded iron (28%), wustite (12%), magnetite (20%) and oxihydroxides (40%). A possible ore source containing 84% FeO, 7% of Al₂O₃ and SiO₂ (all in wt.%) and minor impurities is located a few kilometers from the furnace site, yielding a Mössbauer spectrum consisting of hematite (70%) and oxihydroxides (30%).     

Mössbauer study of nano-TiO2 doped with Fe

A Mössbauer study of nano-TiO₂ doped with Fe is presented. The samples are prepared by sol-gel method, doping Fe by 5, 10 and 15 wt.%, respectively, which are measured with XRD, TEM and Raman spectra. Especially, Mössbauer spectra are emphasized in this study. The anatase phase is major in both doped and no-doped sample. The α-Fe₂O₃ phase is also in the doped samples. The grain size of doped sample is in 5–20 nm range, the major grains are about 13 nm. And the grain size of no-doped sample is about 8 nm. Studying Mössbauer spectra and Raman spectra, we concluded that in the doping process the Fe³⁺ ions entered anatase lattice and substituted Ti⁴⁺ ions. However, the amount of Fe ions in the site is limited to about 1.5 wt.%. It does not increase as the doping Fe increase. The more Fe doped, the more α-Fe₂O₃ formed. For comparing conveniently, it also can be described as (Ti_0.98Fe_0.02)O₂ by atomic percent.     

Studies of Nanosized Iron-Doped TiO<Subscript>2</Subscript> Photocatalysts by Spectroscopic Methods

Iron-doped TiO₂ nanoparticles with iron content in the range of 0.005 < Fe/Ti < 0.3 were prepared using the flame spray pyrolysis method and investigated with CW X-band electron paramagnetic resonance (EPR), X-ray diffraction, and Fourier transform infrared spectroscopy. This allowed for the clarification of the internal organization of Fe–TiO₂ nanoparticles. Different types of Fe(III) centers were distinguished in the samples: isolated high-spin paramagnetic Fe(III) ions (S = 5/2) in rhombic ligand fields state at 0.005 < Fe/Ti < 0.05, and Fe(III) ferromagnetic clusters at Fe/Ti < 0.1. All Fe-doped samples had rather high activity for the photocatalytic mineralization of oxalic acid under visible light illumination (λ > 400 nm) at 25 °C. Correlations were made between EPR and photocatalytic activity results. The specific surface area [S] data allowed us to deduce that the isolated Fe(III) centers were responsible for the photomineralisation of oxalic acid, while the Fe(III) ferromagnetic aggregates decreased the total efficiency of the system.     

Iron-zirconium oxide catalysts for the hydrogenation of carbon monoxide: In situ studies by iron-57 Mössbauer spectroscopy

Some unsupported iron-zirconium oxide catalysts have been prepared by the calcination in air of precipitates containing 15 mole % iron. The catalyst formed at 500°C was shown by powder X-ray diffraction to consist of a non-equilibriated solid solution of iron(III) in a tetragonal or cubic zirconium dioxide structure whereas the catalyst formed at 1000°C was found to contain a zirconium-doped α-iron(III) oxide, or a magnetically ordered iron-zirconium oxide, in combination with an iron-containing monoclinic polymorph of zirconium dioxide. The⁵⁷Fe Mössbauer spectra recorded in situ following the pretreatment of the solids in nitrogen, carbon monoxide and hydrogen showed that little change is induced in the catalysts under such conditions. The⁵⁷Fe Mössbauer spectra also showed that the pretreated catalysts were unchanged by exposure to a 1:1 mixture of carbon monoxide and hydrogen at 270°C and 1 atmosphere pressure but were partially converted to iron carbide when used for the hydrogenation of carbon monoxide at 330°C and at 20 atmospheres pressure. The hydrocarbon product distribution showed Schulz-Flory α-values of 0.73 to 0.76 which were higher than the α-values obtained from pure iron catalysts which had been prepared and pretreated in a similar fashion. The⁵⁷Fe Mössbauer spectra and the results of the catalytic evaluation may be associated with an interaction between zirconium(IV) and the electron-rich atoms of the reactant carbon monoxide.     

Mössbauer and XRD study of pulse plated Fe–P and Fe–Ni thin layers

⁵⁷Fe conversion electron Mössbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe–P and Ni–Fe coatings. XRD and ⁵⁷Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe–P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe–P deposits pulse plated at medium long deposition time (t _on?=?2 ms), with short relaxation time (t _off?=?9 ms) and low current density (I _p?=?0.05 Acm^?2) or at short deposition time (t _on?=?1 ms) with long relaxation time (t _off?=?250 ms) and high current density (I _p?=?1.0 Acm^?2). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni–Fe alloy with a very fine, 5–8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni–Fe and Fe–P pulse plated thin layers.     

A Mössbauer investigation of zirconium distribution and diffusion in ball milled nanocrystalline iron powders

Ball milled nanocrystalline iron with minor zirconium additions was examined using ⁵⁷Fe Mössbauer spectroscopy and X-ray diffraction. Powder samples were synthesized using 0, 5, and 10 wt.% zirconium additions and milled at room temperature for periods up to 24 h. Progressive decrease in grain size as determined by X-ray diffraction was observed as a function of milling time. Mössbauer spectroscopy indicates increased iron-zirconium coordination with increased milling time. After milling, the powder samples were then heat treated in an inert atmosphere of argon at up to 925 K for various times up to 25 min. Analysis of X-ray peak line width (FWHM) was used to characterize grain size and grain growth kinetics as a function of heat treatment, milling time, and alloy content and reveal an increasingly finer post-heated structure in the alloy samples containing more zirconium. Mössbauer measurements were made and suggest Zr is steadily distributed into the Fe lattice with milling and rapidly diffuses to the grain boundaries with heat treatment. The impurity-rich grain boundaries appear to considerably stabilize the refined structure.     

Performance enforcement of gel polymer electrolyte for lithium ion battery with co-doping silicon dioxide and zirconium dioxide nanoparticles

In this work, we report a new method to enforce the comprehensive performances of gel polymer electrolyte (GPE) for lithium ion battery. Poly(methyl methacrylate-acrylonitrile-vinyl acetate) [P(MMA-AN-VAc)] is synthesized as polymer matrix. The physical and electrochemical performances of the matrix and the corresponding GPEs, doped with nano-SiO₂ and nano-ZrO₂ particles individually or simultaneously, are investigated by scanning electron microscopy, thermogravimetry, electrochemical impedance spectroscopy, and charge/discharge test. It is found that the membrane co-doped with 5 wt.% nano-SiO₂?+?5 wt.% nano-ZrO₂ and the corresponding GPE combine the advantages of those doped individually with 10 wt.% nano-SiO₂ or 10 wt.% nano-ZrO₂. Accordingly, the comprehensive performances of the membrane and the corresponding GPE, in terms of thermal stability, ionic conductivity, and electrochemical stability on the anode and cathode of lithium ion battery, is enforced by co-doping 5 wt.% nano-SiO₂ and 5 wt.% nano-ZrO₂.     

Impact of active phase chemical composition and dispersity on catalytic behavior in PROX reaction

Iron and iron-platinum catalysts supported on activated carbon have been successfully synthesized by wet impregnation method and low-temperature treatment in inert atmosphere. The content of the supported phases corresponds to 10 wt % Fe and 0.5 wt % Pt. Four catalytic samples were synthesized: Sample A—activated carbon impregnated with Fe nitrate; Sample B—activated carbon impregnated with Pt salt; Sample C—activated carbon impregnated consequently with Fe and Pt salts; Sample D—activated carbon impregnated simultaneously with Fe and Pt salts. The as-prepared materials were characterized by Mössbauer spectroscopy, X-ray diffraction, infrared and X-ray photoelectron spectroscopy. The spectra show that the activated carbon support and the preparation procedure give rise to the synthesis of isolated metal Pt ions and ultradispersed Fe and Pt oxide species. Probably the presence of different functional groups of activated carbon gives rise to registered very high dispersion of loaded species on support. The catalytic tests were carried out in PROX reaction. A lower activity of bimetallic Pt-Fe samples was explained with the increase in surface oxygen species as a result of predomination of iron oxide on the support leading to the increase in selectivity to the H₂ oxidation. Partial agglomeration of supported iron oxide phase was registered after catalytic tests.     

Examination of the distribution of the tensile deformation systems in tension and tension-creep of Ti-6Al-4V (wt.%) at 296 K and 728 K

The deformation behaviour of an α + β Ti–6Al–4V (wt.%) alloy was investigated during in situ deformation inside a scanning electron microscopy (SEM). Tensile experiments were performed at 296 and 728 K (~0.4Tm), while a tensile-creep experiment was performed at 728 K and 310 MPa (σ/σ_ys = 0.74). The active deformation systems were identified using electron backscattered diffraction-based slip-trace analysis and SEM images of the specimen surface. The distribution of the active deformation systems varied as a function of temperature. Basal slip deformation played a major role in the tensile deformation behaviour, and the relative activity of basal slip increased with increasing temperature. For the 296 K tension deformation, basal slip was less active than prismatic slip, whereas this was reversed at 728 K. Twinning was observed in both the 296 and 728 K tension experiments; however, no more than 4% of the total deformation systems observed was twins. The tension-creep experiment revealed no slip traces, however grain boundary ledge formation was observed, suggesting that grain boundary sliding was an active deformation mechanism. The results of this work were compared with those from previous studies on commercially pure Ti, Ti–5Al–2.5Sn (wt.%) and Ti–8Al–1Mo–1V (wt.%), and the effects of alloying on the deformation behaviour are discussed. The relative amount of basal slip activity increased with increasing Al content.     

Structural and Mössbauer studies of aerosol FeCu nanoparticles in a wide composition range

Structure and magnetic state of aerosol FeCu nanoparticles of 10–30 nm size with Cu content of 0.6–92.1 at.% have been examined by X-ray diffraction and Mössbauer spectroscopy. The FeCu particles have been shown to consist of an iron core surrounded by a copper and Fe oxide shell. With increasing Cu content the iron core having a bcc structure is reduced down to its complete disappearance followed by vanishing ferromagnetism of the particles. Within the copper content from 4.9 to 74.3 at.% the bcc and fcc phases coexist, with the fcc phase having a lattice constant close to that of pure copper and the bcc lattice constant being slightly higher than that for pure Fe due to embedding Cu atoms into the Fe lattice. At Fe-rich FeCu samples a presence of two-spin (ferromagnetic and paramagnetic) components of the fcc Fe is also observed. In the case of a thin copper shell there is only the ferromagnetic fcc Fe, whereas with further thickening of the shell both spin states of the fcc Fe appear existing up to a 20% Cu content. For FeCu samples with a higher Cu content they disappear due to oxidation of the copper grains. The Cu-rich samples with Cu content higher 80 at.% have a fcc structure, with the lattice constant being slightly higher than that of copper and they are paramagnetic. A slight increase of the lattice constant is due to the penetration of small iron aggregations into the Cu grains. In contact with air, the FeCu particles become covered with Fe₃O₄ and Cu₂O. Their long-term exposure to ambient conditions leads to further oxidation process of Cu₂O to CuO.     

Design of an Auger Electron Mössbauer Spectrometer (AEMS) using a modified cylindrical mirror analyzer

We have designed and built an Auger Electron Mössbauer Spectrometer (AEMS) for the detection of resonant ⁵⁷Fe Auger electrons using a modified commercial cylindrical mirror analyzer (CMA). The CMA final aperture was modified intentionally in order to increase electron transmission at the expense of reducing its energy resolution, from an original value of 0.5 % to a value of 11 % after the modification. The Channeltron detector electronics and the pre-amplifier were also modified in order to increase the counting efficiency. The electron energy analyzer is selective in energy in the 30 eV–3000 eV range, so the spectrometer can be used to detect MNN (45 eV) and LMM (600–700 eV) Fe Auger signals, what gives it a high surface sensitivity for Fe containing samples. We have used it to acquire the Fe LMM Auger signals generated from the de-excitation process after γ-Ray resonant nuclear absorption. The spectrometer can be used to study samples non-enriched in ⁵⁷Fe, with acquisition times from 5 to 7 days, what is a big advantage. From electron trajectory Monte Carlo simulations in metallic iron, the mean-escape-depth of the detected Auger signals has been estimated in approximately 1 nm. Fe K conversion electrons and KLL Auger electrons with mean escape depths of 129 nm and 78 nm respectively also contribute to the detected signal although in a lesser proportion.