Effects of sulfur sources on properties of Cu2ZnSnS4 nanoparticles

Three Fe(β-diketonate)₃ compounds namely Fe(tmhd)₃ (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionato), Fe(hfac)₃ (hfac = hexafluoroacetylaceto), and Fe(dbm)₃ (dbm = dibenzoylmethane) were used as substitutes to Fe(acac)₃ (acac = acetyleacetonate) in the synthesis of FePt nanoparticles. The obtained superparamagnetic nanoparticles are 4–5 nm in diameter without showing a large size variation with substituent Fe(β-diketonate)₃. The synchrotron X-ray absorption spectroscopy confirmed the energy dispersive spectroscopy that as-synthesized nanoparticles were composed of iron oxides and metallic FePt₃ alloys. By employing Fe(hfac)₃, the Fe fraction was reduced and the magnetization was modest. The use of Fe(dbm)₃ as starting materials gave rise to densely packed FePt₃/Fe₂O₃ heterodimers. The replacements of Fe(acac)₃ by Fe(tmhd)₃ led to the long-range order of nanoparticle assembly with the narrowest size distribution.     

Synthesis and characterization of L10 FePt nanoparticles from Pt–Fe3O4 core-shell nanoparticles

Pt/Fe₃O₄ core-shell nanoparticles have been prepared by a modified polyol method. Pt nanoparticles were first prepared via the reduction of Pt(acac)₂ by polyethylene glycol-200 (PEG-200), and layers of iron oxide were subsequently deposited on the surface of Pt nanoparticles by the thermal decomposition of Fe(acac)₃. The nanoparticles were characterized by XRD and HR-TEM. The as-prepared Pt/Fe₃O₄ nanoparticles have a chemically disordered FCC structure and transformed into chemically ordered fct structure after annealing in reducing atmosphere (4% H₂, 96% Ar) at 700 °C. The ordered fct FePt phase has high magnetic anisotropy with coercivity reaching 7.5 kOe at room temperature and 9.3 kOe at 10 K.     

Changes in the state of iron atoms in Zr alloys during corrosion tests in an autoclave

Mössbauerinvestigations were carried out on oxide films formed on specimens of zirconium alloys Zr-1.0 %wtFe-1.2 %wtSn-0.5 %wtCr subjected to corrosion in steam-water environment at a temperature of 360 °C and at a pressure of 16.8 MPa with lithium and boron additions, and on Zr-1.4 %wtFe-0.7 %wtCr corroded in steam-water environment at 350 °C and 16.8 MPa as well as in steam-water environment at 500 °C and 10 MPa. In the metal part of the samples, under the oxide film, the iron atoms are in form of intermetallic precipitates of Zr(Fe, Cr)₂. The corrosion process decomposes the intermetallic precipitates and particles are formed of metallic iron with inclusions of chromium atoms –Fe(Cr), α–Fe₂O₃ and Fe₃O₄ compounds. Part of the iron ions are in divalent and part in trivalent paramagnetic states. It is proposed that some part of the iron containing oxide precipitates in the oxide film may be in the form of nanoparticles which pass from the superparamagnetic to the ferromagnetic state with decreasing temperature.     

Growth and magnetic behavior of bismuth substituted yttrium iron garnet nanoparticles

Crystal growth and the magnetic properties of bismuth substituted yttrium iron garnet (Bi-YIG) nanoparticles were studied with particular focus on the bismuth composition dependence of the magnetic properties of the particles and the effects of annealing on the garnet phase formation. The Bi-YIG nanoparticles of 47–67 nm in size can be chemically synthesized when they are annealed at 650–850 °C. Both the lattice constant and the magnetization of the garnet nanoparticles linearly increase when the bismuth composition in the Bi-YIG particles increases. We have found that chemically synthesized nanoparticles transform from the amorphous to the garnet phase when annealed at temperatures below 650 °C, while the onset of magnetic moment of iron in the garnet nanoparticles is observed slightly above 650 °C. According to Mössbauer effect measurements, the hyperfine fields of ⁵⁷Fe at the tetrahedral and octahedral sites in the garnet are 39 and 48 T, respectively.     

Photoelectrochemical properties of texture‐controlled nanostructured α‐Fe2O3 thin films prepared by AACVD

Nanostructured α‐Fe₂O₃ thin film electrodes were deposited by aerosol‐assisted chemical vapour deposition (AACVD) for photoelectrochemical (PEC) water splitting on conducting glass substrates using 0.1 M methanolic solution of Fe(acac)₃. The XRD analysis confirmed that the films are highly crystalline α‐Fe₂O₃ and free from other iron oxide phases. The highly reproducible electrodes have an optical bandgap of ～2.15 eV and exhibit anodic photocurrent. The current–voltage characterization of the electrodes reveals that the photocurrent density strongly depended on the film morphology and deposition temperature. Scanning electron microscopy (SEM) analysis showed a change in the surface morphology with the change in deposition temperature. The films deposited at 450 °C have nanoporous structures which provide a maximum electrode/electrolyte interface. The maximum photocurrent density of 455 µA/cm² was achieved at 0.25 V vs. Ag/AgCl/3M KCl (～1.23 V vs. RHE) and the incident photon to electron conversion efficiency (IPCE) was 23.6% at 350 nm for the electrode deposited at 450 °C. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Magnetic behaviour and DCEMS study of SnO2 films implanted with 57Fe

Fe implanted SnO₂ films (5 × 10¹⁶ and 1 × 10^{17 57}Fe ions/cm²) characterized by conversion electron Mossbauer spectroscopy (CEMS) are reviewed. The substrate temperatures affect the growth of precipitated iron oxides. The Fe ion implanted film at room temperature (RT) shows no Kerr effect and no magnetic sextet in CEM spectra. The SnO₂ film implanted with ⁵⁷Fe at the substrate temperature of 300 °C show a small Kerr effect although the magnetic sextet is not observed, but post-annealing results in the disappearance of the Kerr effect. This magnetism is considered to be due to defect induced magnetism. Some samples were measured by CEMS at 15 K. SnO₂ (0.1 at %Sb and 3 at %Sb) films, implanted at 500 °C and the post-annealed samples, show RT ferromagnetism due to formation of clusters of magnetite and maghemite, respectively. The layer by layer analysis of these films within 100 nm in thickness has been done by depth sensitive CEMS (DCEMS) using a He + 5 % CH₄ gas counter. The structures and compositions of Fe implanted SnO₂ films, and the effects due to post-annealing were investigated.     

Synthesis, Crystal Structure and Photoluminescence of a Cyclometalated Iridium(III) Coumarin Complex

In this paper a new cyclometalated iridium(III) coumarin complex, Ir(III)bis(3-(2-benzothiazolyl)coumarinato N,C⁴)(acetylacetonate) (Ir(L)₂(acac)), was synthesized and characterized. X-ray crystallography demonstrated that the iridium(III) ion is hexacoordinated by two C atoms and two N atoms from 3-(2-benzothiazolyl)coumarinato ligands and two O atoms from acac ligand, displaying distorted octahedral coordination geometry. The Ir(L)₂(acac) complex has good thermal stability with less than 2 % weight-reduction occurring at 300 °C, and exhibits strong reddish orange emission. The results shown that Ir(L)₂(acac) is useful for fabrication organic light-emitting diodes.     

The effects of vacuum annealing on the structure and surface chemistry of iron nanoparticles

In order to increase the longevity of contaminant retention, a method is sought to improve the corrosion resistance of iron nanoparticles (INP) used for remediation of contaminated water and thereby extend their industrial lifetime. A multi-disciplinary approach was used to investigate changes induced by vacuum annealing (<5 × 10^?8 mbar) at 500 °C on the bulk and surface chemistry of INP. The particle size did not change significantly as a result of annealing but the surface oxide thickness decreased from an average of 3–4 nm to 2 nm. BET analysis recorded a decrease in INP surface area from 19.0 to 4.8 m² g^?1, consistent with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations which indicated the diffusion bonding of previously discrete particles at points of contact. X-ray diffraction (XRD) confirmed that recrystallisation of the metallic cores had occurred, converting a significant fraction of poorly crystalline iron to bcc α-Fe and Fe₂B phases. X-ray photoelectron spectroscopy (XPS) indicated a change in the surface oxide stoichiometry from magnetite (Fe₃O₄) towards wüstite (FeO) and the migration of boron and carbon to the particle surfaces. The improved core crystallinity and the presence of passivating impurity phases at the INP surfaces may act to improve the corrosion resistance and reactive lifespan of the vacuum annealed INP for environmental applications.     

Laser induced breakdown spectroscopy surface analysis correlated with the process of nanoparticle production by laser ablation in liquids

Linkage isomerism is the coexistence of iso-compositional molecules or solids differing by connectivity of the metal to a ligand. In a crystalline solid state, the rotation is possible for asymmetric ligands, e.g., for cyanide ligand. Here we report on our observation of a phase transition in anhydrous RbMn[Fe(CN)₆] (nearly stoichiometric) and on the effect of linkage isomerism ensuing our interpretation of the results of Mössbauer study in which we observe the iron spin state crossover among two phases involved into this transition. The anhydrous RbMn[Fe(CN)₆] can be prepared via prolonged thermal treatment (1 week at at 80 °C) of the as-synthesized hydrated RbMn[Fe(CN)₆]·H₂O. The latter compound famous for its charge-transfer phase transition is a precursor in our case. As the temperature is raising above 80 °C (remaining below 100 °C) we observe RbMn[Fe(CN)₆] that inherited its F-43 m symmetry from RbMn[Fe(CN)₆]·H₂O transforming to a phase of the Fm-3 m symmetry. In the latter, more than half of Fe^3?+? ions are in high-spin state. We suggest a plausible way to explain the spin-crossover that is to allow the linkage isomerism by rotation of the cyanide ligands.     

Comparison of Eu(NO<Subscript>3</Subscript>)<Subscript>3</Subscript> and Eu(acac)<Subscript>3</Subscript> precursors for doping luminescent silica nanoparticles

In this study, we report the comparison between Eu³⁺-doped silica nanoparticles synthesized by Stöber method using Eu(NO₃)₃ or Eu(acac)₃ as precursors. The impact of different europium species on the properties of the final silica nanospheres is investigated in details in terms of size, morphology, reachable doping amount, and luminescence efficiency. Moreover, the results obtained for different thermal treatments are presented and discussed. It is shown that the organic complex modify the silica growing process, leading to bigger and irregular nanoparticles (500–800 nm) with respect to the perfectly spherical ones (400 nm) obtained by the nitrate salt, but their luminescence intensity and lifetime is significantly higher when 800–900 °C annealing is performed.     

M?ssbauer study of carbon coated iron magnetic nanoparticles produced by simultaneous reduction/pyrolysis

Magnetic iron nanoparticles immersed in a carbon matrix were produced by a combined process of controlled dispersion of Fe^3?+? ions in sucrose, thermal decomposition with simultaneous reduction of iron cores and the formation of the porous carbonaceous matrix. The materials were prepared with iron contents of 1, 4 and 8 in %wt in sucrose and heated at 400, 600 and 800°. The samples were analyzed by XRD, Mössbauer spectroscopy, magnetization measurements, TG, SEM and TEM. The materials prepared at 400° are composed essentially of Fe₃O₄ particles and carbon, while treatments at higher temperatures, e.g. 600 and 800° produced as main phases Fe⁰ and Fe₃C. The Mössbauer spectra of samples heated at 400° showed two sextets characteristic of a magnetite phase and other contributions compatible with Fe^3?+? and Fe^2?+? phases in a carbonaceous matrix. Samples treated at temperatures above 600° showed the presence of metallic iron with concentrations between 16?C43%. The samples heated at 800° produced higher amounts of Fe₃C (between 20% and 58%). SEM showed for the iron 8% sample treated at 600?C800°C particle sizes smaller than 50 nm. Due to the presence of Fe⁰ particles in the carbonaceous porous matrix the materials have great potential for application as magnetic adsorbents.     

Engineering the Internal Structure of Magnetic Silica Nanoparticles by Thermal Control

Calcination of hydrated iron salts in the pores of both spherical and rod‐shaped mesoporous silica nanoparticles (NPs) changes the internal structure from an ordered 2D hexagonal structure into a smaller number of large voids in the particles with sizes ranging from large hollow cores down to ten nanometer voids. The voids only form when the heating rate is rapid at a rate of 30 °C min^?1. The sizes of the voids are controlled reproducibly by the final calcination temperature; as the temperature is decreased the number of voids decreases as their size increases. The phase of the iron oxide NPs is α‐Fe₂O₃ when annealed at 500 °C, and Fe₃O₄ when annealed at lower temperatures. The water molecules in the hydrated iron (III) chloride precursor salts appear to play important roles by hydrolyzing Si? O? Si bonding, and the resulting silanol is mobile enough to affect the reconstruction into the framed hollow structures at high temperature. Along with hexahydrates, trivalent Fe³⁺ ions are assumed to contribute to the structure disruption of mesoporous silica by replacing tetrahedral Si⁴⁺ ions and making Fe? O? Si bonding. Volume fraction tomography images generated from transmission electron microscopy (TEM) images enable precise visualization of the structures. These results provide a controllable method of engineering the internal shapes in silica matrices containing superparamagnetic NPs.     

Supported iron based redox systems for hydrogen production and storage from ethanol

Hydrogen production using ethanol and Fe₂O₃/support in a redox cycle was investigated. The composites were prepared by impregnation of Al₂O₃ and SiO₂ with Fe(NO₃)₃, with different proportions of iron, i.e. 10, 30 and 50 wt.%, calcinated at 450°C and characterized by Mössbauer spectroscopy, XRD, SEM, BET and TG. The redox cycle to produce and/or store hydrogen is a two step process (1) initially the ethanol is used to reduce the iron oxide to Fe°; (2) and when H₂ is needed, Fe° reacts with H₂O to produce CO-free hydrogen, and the iron oxide is reduced again to Fe° making this system cyclic. After the reactions it was interesting to observe that ethanol can directly reduce the iron oxide to produce metallic iron, with carbon deposition and iron–carbon as side product. Preliminary results indicate that it is possible to perform multiple redox cycles with the supported iron oxide without deactivation.     

Effect of Fe2O3 nanoparticles on combustion of coal surrogate (Anisole): Enhanced ignition and formation of persistent free radicals

This contribution explores the effect of nanoparticles of iron (III) oxide (Fe₂O₃) on the combustion of coal surrogate, i.e., anisole, identifying the changes in ignition features as well as the occurrence of persistent organic pollutants in the initiation channels. The method applies packed-bed reactor coupled with Fourier transform infrared (FTIR) spectroscopy to quantitate the ignition temperature under typical fuel-rich conditions, in-situ electron paramagnetic resonance (EPR) to elucidate the formation of environmentally-persistent free radicals (EPFR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the chemisorption of organic substrates on the nanoparticles, as well as X-ray diffraction for particles characterisation (PXRD). We employ cluster-based quantum mechanical calculation to map the reaction pathway within the scope of the density functional theory. The results of Fe₂O₃-mediated combustion of anisole depict an excessive reduction in ignition temperature from 500?°C around 220?°C at λ?=?0.8. As confirmed both from EPR and DRIFTS measurements, the chemisorption of anisole on α-Fe₂O₃ surfaces follows the direct dissociation of the O–CH₃ (and OCH₂–H), leading to the formation of surface-bound phenoxy radicals at temperatures as low as 25?°C and incurring an estimated energy barrier of E_a?=?18?kJ mol^?1 and a preexponential factor of A?=?2.7?×?10¹² M^?1 s^?1. This insight applies to free-radical chain reactions that induce spontaneous fires of coal, as coal comprises ferric oxide nanoparticles, and equally to coexistence of aromatic fuels with thermodynamically reactive Fe₂O₃ surface, e.g., in fly ash, at the cooled-down tail of combustion stacks.     

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.     

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.     

The Fe–Fe2P phase diagram at 6 GPa

Here, we report experimental results on melting and subsolidus phase relations in the Fe–Fe₂P system at 6?GPa and 900–1600°C. The system has two P-bearing compounds: Fe₃P and Fe₂P. X-ray diffraction patterns of these compounds correspond to schreibersite and barringerite, respectively. The Fe–Fe₃P eutectic appears at 1075°C and 16?mol% P. Schreibersite (Fe₃P) melts incongruently at 1250°C to produce barringerite (Fe₂P) and liquid containing 23?mol% P. Barringerite (Fe₂P) melts congruently at 1575°C. Maximum solid solution of P in metallic iron at 6?GPa is 5?mol%. As temperature increases to 1600°C, the P solubility in the metallic iron decreases to 0.5?mol%, whereas the P content in coexisting liquid decreases to 3?mol%. The composition of quenched phases from Fe–P melt coincides with the compositions of equilibrium phases at corresponding temperature. Consequently, the composition of quenched products of Fe-P melts in meteorites can be used for reconstruction of P–T conditions of their crystallization under ambient or low pressures or during shock melting by impact collisions.     

A correlation between structural and optical properties of cobalt oxide nanoparticles for various annealing conditions

Two stable phases of cobalt oxide nanoparticles of controlled sizes have been synthesized using environmentally friendly inorganic precursor. Structural characterization using X-ray diffraction (XRD) shows a single-phase spinal Co₃O₄ structure up to annealing temperature of 800 °C and a mixed phase of Co₃O₄ and CoO particles for T>900 °C. Single-phase CoO nanoparticles are also obtained by annealing the particles at a temperature >900 °C and cooling in inert atmosphere. Average macro- and micro-strain were estimated using XRD data. Macrostrain was found to be the minimum for particles annealed at 600 °C, whereas microstrain was found to decrease with increasing annealing temperature up to 900 °C. A correlation between the density of localized states (DOS) in the band gap and strain is expected because the origin of both strain and DOS are defects and bond length distortions. Sub-gap absorption measurement and model calculations have been used for the determination of DOS. For cobalt oxide nanoparticle samples we find a correlation between estimated strain and density of states in the band gap.     

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).     

The effects of vacuum annealing on the structure and surface chemistry of iron:nickel alloy nanoparticles

In order to increase the longevity of contaminant retention on the particle surface, a method is sought to improve the corrosion resistance of bimetallic iron nickel nanoparticles (INNP) used for the remediation of contaminated water, and thereby extend their industrial lifetime. A multi-disciplinary approach was used to investigate changes induced by vacuum annealing (<5 × 10^?8 mbar) at 500 °C on the bulk and surface chemistry of INNP. The particle size was determined to increase significantly as a result of annealing and the thickness of the surface oxide increased by 50%. BET analysis recorded a decrease in INP surface area from 44.88 to 8.08 m² g^?1, consistent with observations from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) which indicated the diffusion bonding of previously discrete particles at points of contact. X-ray diffraction (XRD) confirmed that recrystallisation of the metallic cores had occurred, converting a significant fraction of initially amorphous iron nickel alloy into crystalline FeNi alloy. X-ray photoelectron spectroscopy (XPS) indicated a reduction in the proportion of surface iron oxide and a change in its stoichiometry related to annealing-induced disproportionation. This was also evidenced by an increased proportion of Fe(0) and Ni(0) to Fe- and Ni-oxides, respectively. The data also indicated the concurrent development of boron oxide at the metal surfaces, which accounts for the overall increase measured in surface oxide thickness. The improved core crystallinity and the presence of passivating impurity phases at the INNP surfaces may act to improve the corrosion resistance and reactive lifespan of the vacuum annealed INNP for environmental applications.