Structural, calorimetric and magnetic properties study of the Cu0,91Fe0,09O system

In this work the Cu_0.91Fe_0.09O nanocrystalline system was prepared via the co-precipitation method. Using Mössbauer Spectrometry, X-Ray Diffraction, Vibrating Sample Magnetometry, Thermogravimetry and Differential Scanning Calorimetry, we study the magnetic behavior, and the structural and calorimetric properties of this system. X-ray diffraction shows only the presence of the CuO structural monoclinic phase, suggesting that Cu atoms are substituted by Fe ones. This hypothesis was confirmed by Mössbauer spectrometry at room temperature, because it shows that the spectrum is formed by two doublets, which correspond to Fe^?+?2 and Fe^?+?3 sites. Hysteresis cycles obtained by vibrating sample magnetometry detect a soft ferromagnetic behavior at room temperature with coercive fields between 8 and 20 Oe. At T = 20 K the sample shows a hard-magnetic behavior. The thermogravimetry results show a Néel temperature (T _N > 440 °C). The differential scanning calorimetry curve show two endothermic peaks in the 90–120 °C range.     

ZnO-Fe3O4 composite prepared by sol-gel method with H2 deoxidation

Fe doped ZnO powder samples (Fe/Zn=0.05 and 0.1) were prepared by sol-gel method with H₂ deoxidation at 450 ^°C for several hours or just heated in air at the same temperature. It was showed by vibrating sample magnetometer (VSM) that samples heat treated in H₂ could show strong ferromagnetism at room temperature while samples treated in air only show very weak magnetism. XRD using Co kα X-ray revealed that the samples heated in H₂ were not pure phase but like a granular system and the magnetism mainly results from Fe₃O₄ in samples while samples heated in air showed pure ZnO phase. Our work indicated that H₂ deoxidation treatment may be an effective technique to fabricate such magnetic semiconductor-like materials with Curie temperature higher than room temperature.     

Synthesis and gas sensing properties of perovskite CdSnO<Subscript>3</Subscript> nanoparticles

The CdSnO₃ semiconducting oxide that can be used as a gas-sensitive material for detecting ethanol gas is reported in this paper. CdSnO₃ nanoparticles were prepared by a chemical co-precipitation synthesis method, in which the preparation conditions were carefully controlled. The n-type gas-sensing semiconductors were obtained from the as-synthesized powders calcined at 600°C for 1 h. The phase and microstructure of the obtained nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET) method with a gas adsorption analyzer. CdSnO₃ has a small particle size range of 30–50 nm and a high surface area of 9.12 m²/g, and a uniformity global shape. The gas sensitivity and operating temperature, and selectivity of CdSnO₃-based sensors were measured in detail. The gas sensors fabricated by CdSnO₃ nanoparticles had good sensitivity and selectivity to vapor of C₂H₅OH when working temperature at 267°C, the value of gas sensitivity at 100 ppm of C₂H₅OH gas can reach 11.2 times. Furthermore, gas-sensing mechanism was studied by using chromatographic analysis.     

Local structure and water cleaning ability of iron oxide nanoparticles prepared by hydro-thermal reaction

Nanoparticles (NPs) of Fe₃O₄ and γFe₂O₃ synthesized by hydrothermal reaction were characterized by X-ray diffractometry (XRD), ⁵⁷Fe-Mössbauer spectroscopy and field emission scanning electron microscopy (FE-SEM). A decrease in concentration of methylene blue (MB) aqueous solution due to bulk Fe⁰-NP γFe₂O₃ mixture with the mass ratio of 3:7 was measured by ultraviolet-visible light absorption spectroscopy (UV-Vis). The Mössbauer spectrum of NP Fe₃O₄ prepared from hydrothermal reaction was composed of two sextets with absorption area (A), isomer shift (δ) and internal magnetic field (H _int) of 56.3 %, 0.34_±0.03 mm s^???1 and 49.0_±0.30 T for tetrahedral (T _d) Fe^III, and 43.7 %, 0.66_±0.11 mm s^???1 and 44.0_±0.71 T for octahedral (O _h) Fe^II?+?III. The Fe^II/Fe^III ratio was determined to be 0.280 for NP Fe₃O₄, giving ‘x’ of 0.124 in Fe_3???xO_4. These results show that NP Fe₃O₄ prepared by hydrothermal reaction was not regular but nonstoichiometric Fe₃O₄. Consistent results were observed for XRD patterns of NP Fe_3???xO₄ indicating sharp intense peaks at 2Θ of 30.2, 35.7 and 43.3° with a large linewidth of 0.44°, yielding the crystallite size of 29–37 nm from the Scherrer’s equation. Iso-thermal annealing of NP Fe_3???xO₄ at 250 °C for 30 min resulted in the precipitation of NP γFe₂O₃ with δ of 0.33_±0.03 mm s^???1 and H _intof 46.4_±0.27 T due to magnetic tetrahedral Fe^III. The Debye temperature of NP Fe_3???xO₄ was respectively estimated to be 267_±5.45 K for Fe $^{\mathrm{III}}(T_{\mathrm{d}})$ and 282_±7.17 K for Fe $^{\mathrm{II+III}}(O_{\mathrm{h}})$ , both of which were smaller than that obtained for bulk Fe₃O₄ of 280_±4.15 K and 307_±5.70 K, indicating that the chemical environment of iron of NPs is less rigid than that of the bulk compounds. A leaching test using methylene blue (MB) and mixture of bulk Fe⁰-NP γFe₂O₃ (3:7) showed a remarkable decrease in MB concentration from 1.90 × 10^???2 to 9.49 × 10^???4 mM for 24 h with the first order rate constant (k _MB) of 2.1 × 10^???3 min^???1. This result verifies that MB decomposing ability is enhanced by using NP γFe₂O₃ compared with the k _MB of 1.1 × 10^???4 min^???1 previously obtained from the leaching test using MB and bulk mixture of Fe⁰???γFe₂O₃ (3:7).     

Synthesis and electric properties of perovskite Pr0.6Ca0.4Fe0.8Co0.2O3 for SOFC applications

In this study, polycrystalline powder Pr_0.6Ca_0.4Fe_0.8Co_0.2O₃ (PCFC) was synthesized by a sol–gel process. This oxide was analyzed by X-ray powder diffraction. Synthesized Pr_0.6Ca_0.4Fe_0.8Co_0.2O₃ showed up to be single phase and belongs to the orthorhombic crystalline system with a Pbnm space group. The microstructural features of the synthesized products display particles having an irregular morphology and a size in the range of 50–100 nm. X-ray diffraction (XRD) analysis shows the chemical compatibility between the PCFC cathode and the electrolyte Sm-doped ceria since no reaction products were honored when the material was mixed and co-fired at 1,000 °C for 168 h. The thermal expansion coefficient of PCFC 16.9?×?10^?6 °C^?1 is slightly higher than that of Ce_0.8Sm_0.2O_1.9 (SDC) over the studied temperature range. The greater contribution to the total resistance of the electrode is the electrochemical resistance associated with oxygen exchange in the cathode surface (0.96 Ωcm²). The dc four-probe measurement indicated that PCFC exhibits fairly high electrical conductivity, over 100 S cm^?1 at T?≥?500 °C, making this material promising as a cathode material for intermediate temperature solid oxide fuel cells.     

Novel nanocomposite membranes based on polybenzimidazole and Fe<Subscript>2</Subscript>TiO<Subscript>5</Subscript> nanoparticles for proton exchange membrane fuel cells

In this work, Fe₂TiO₅ nanoparticles were used for improving the proton conductivity, and water and acid uptake of polybenzimidazole (PBI)-based proton exchange membranes. The nanocomposite membranes have been prepared using different amounts of Fe₂TiO₅ nanoparticles and dispersed into a PBI membrane with the solution-casting method. The prepared membranes were then physico-chemically and electrochemically characterized for use as electrolytes in high-temperature PEMFCs. The PBI/Fe₂TiO₅ membranes (PFT) showed a higher acid uptake and proton conductivity compared with the pure PBI membranes. The highest acid uptake (156 %) and proton conductivity (78 mS/cm at 180 °C) were observed for the PBI nanocomposite membranes containing 4 wt% of Fe₂TiO₅ nanoparticles (PFT₄). The PFT₄ composite membrane showed 380 mW/cm² power density and 760 mA/cm² current density in 0.5 V at 180 °C at dry condition. The above results indicated that the PFT₄ nanocomposite membranes could be utilized as proton exchange membranes for high-temperature fuel cells.     

Investigation of Ce0.9Sr0.1Cr0.5Co0.5O3−δ as the anode material for solid oxide fuel cells fueled with H2S

Ce_0.9Sr_0.1Cr_0.5Co_0.5O_3?δ (CSCrCo) as an anode catalyst was studied in a solid oxide fuel cell (SOFC), where hydrogen sulfide (H₂S) was used as fuel. The conductivities were evaluated with a four-probe DC technique in 3 % H₂-N₂ and 5 % H₂S-N₂ at 570–800 °C, respectively. X-ray diffraction (XRD) patterns show that CSCrCo powders are fluorite structure which is similar to that of CeO₂ parent (JCPDS card no. 34-0394). Meanwhile, CSCrCo anode material has good chemical compatibility with electrolyte (Ce_0.8Sm_0.2O_1.9 (SDC)) in N₂. Through the analysis of XRD and Fourier transform infrared patterns, no other new phase is detected after treatment in 5 % H₂S-N₂ at 800 °C for 5 h, which indicate that the material has a good sulfur tolerance. H₂ temperature-programmed reduction and Tafel curves indicate that the temperature of the best catalytic activity is 600 °C. The electrochemical properties of the cell comprising CSCrCo-SDC/SDC/Ag are measured in 5 % H₂S-N₂ at low temperatures (500 and 600 °C). The maximal open circuit voltage is 1.04 V, the maximal power density is 12.55 mW cm^?2, and the maximal current density is 40 mA cm^?2 at 500 °C. While at 600 °C, the corresponding values are 0.95 V, 14.21 mW cm^?2, and 90.01 mA cm^?2, respectively. After SOFC operating in 5 % H₂S, X-ray photoelectron spectroscopy is used to compare the fresh sample with the H₂S-treated one.     

Dependence of the selectivity of SnO2 nanorod gas sensors on functionalization materials

Effects of functionalization materials on the selectivity of SnO₂ nanorod gas sensors were examined by comparing the responses of SnO₂ one-dimensional nanostructures functionalized with CuO and Pd to ethanol and H₂S gases. The response of pristine SnO₂ nanorods to 500 ppm ethanol was similar to 100 ppm H₂S. CuO-functionalized SnO₂ nanorods showed a slightly stronger response to 100 ppm H₂S than to 500 ppm ethanol. In contrast, Pd-functionalized SnO₂ nanorods showed a considerably stronger response to 500 ppm ethanol than to 100 ppm H₂S. In other words, the H₂S selectivity of SnO₂ nanorods over ethanol is enhanced by functionalization with CuO, whereas the ethanol selectivity of SnO₂ nanorods over H₂S is enhanced by functionalization with Pd. This result shows that the selectivity of SnO₂ nanorods depends strongly on the functionalization material. The ethanol and H₂S gas sensing mechanisms of CuO- and Pd-functionalized SnO₂ nanorods are also discussed.     

CEMS study on diluted magneto titanium oxide films prepared by pulsed laser deposition

6% ⁵⁷Fe doped titanium oxide films, prepared by pulsed laser deposition (PLD) on sapphire substrate at 650°C under various vacuum conditions, were characterized mainly by conversion electron Mössbauer spectrometry (CEMS). Two magnetic sextets with hyperfine fields 33 and 29 T, and one doublet were observed in the CEMS spectra of TiO₂ films prepared under PO₂ = 10^?6 and 10^?8 torr, which showed ferromagnetism at room temperature, whereas only the doublet of paramagnetic Fe³⁺ species was observed for the film prepared under PO₂ = 10^?1 torr.     

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.     

Synthesis and performance of Sm0.9Sr0.1Cr0.5Fe0.5O3 as anode material for SOFCs running on H2S-containing fuel

Sm_0.9Sr_0.1Cr_0.5Fe_0.5O₃ (SSCF) was successfully synthesized by gel combustion method. The structure and physicochemical properties of SSCF were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR). The results showed that SSCF had orthorhombic perovskite-type structure and a homogeneous distribution of pores and particles with grain size in the range 200–300 nm. Meanwhile, SSCF exhibited good chemical compatibility with electrolyte Ce_0.8Sm_0.2O_1.9 (SDC), and no additional diffraction peaks associated with impurities were observed after exposure to 10 %?v/v H₂/N₂ and 1 %?v/v H₂S/N₂. The conductivities of SSCF were evaluated with DC four-probe method in various atmospheres at 400–800 °C. The highest conductivities of SSCF were 0.56, 0.26 and 0.12 S?cm^?1 in air, 10 %?v/v H₂/N₂ and 1 %?v/v H₂S/N₂, respectively. The electrochemical properties were measured for the cell with configuration of SSCF-SDC/SDC/Ag at different temperatures. Electrochemical impedance spectroscopy (EIS) revealed that with the increase in temperature, the ohmic and total interfacial resistances of the cell decreased and the ohmic resistance gradually became the main factor affecting the performance of the cell.     

Synthesis of Au-functionalized SnO2 nanotubes using TeO2 nanowires as templates and their enhanced gas sensing properties

Au-functionalized SnO₂ nanotubes were prepared for use as gas sensors using TeO₂ nanowires as templates. Transmission electron microscopy revealed tube diameters, tube lengths and tube wall thicknesses ranging from 50 to 200 nm, 5 to 50 μm, and 13 to 18 nm, respectively. The Au-functionalized SnO₂ nanotube sensors showed responses of 179–473 % to 1–5 ppm NO₂ at 300 ^°C. These values are much higher than those obtained using bare SnO₂ nanotubes synthesized in this study and most other SnO₂ one-dimensional nanostructure-based sensors reported in the literature. The NO₂ gas sensing mechanism of the Au-functionalized SnO₂ nanotube sensors is also discussed.     

Phase transformation of strontium hexagonal ferrite

The phase transformation of strontium hexagonal ferrite (SrFe₁₂O₁₉) to magnetite (Fe₃O₄) as main phase and strontium carbonate (SrCO₃) as secondary phase is reported here. SrFe₁₂O₁₉ powder was obtained by a heat treatment at 250 °C under controlled oxygen flow. It was observed that the phase transformation occurred when the SrFe₁₂O₁₉ ferrite was heated up to 625 °C in confinement conditions. This transformation took place by a combination of three factors: the presence of stresses in the crystal lattice of SrFe₁₂O₁₉ due to a low synthesis temperature, the reduction of Fe³⁺ to Fe²⁺ during the heating up to 625 °C, and the similarity of the coordination spheres of the iron atoms present in the S-block of SrFe₁₂O₁₉ and Fe₃O₄. X-ray diffraction analysis confirmed the existence of strain and crystal deformation in SrFe₁₂O₁₉ and the absence of them in the material after the phase transformation. Dispersive X-ray absorption spectroscopy and Fe⁵⁷ Mössbauer spectroscopy provided evidences of the reduction of Fe³⁺ to Fe²⁺ in the SrFe₁₂O₁₉ crystal.     

Growth and characterization of oriented cadmium sulphide nanocrystals under Langmuir-Blodgett monolayer of arachidic acid

Cadmium sulphide nanocrystals were grown at room temperature (20 °C) under arachidic acid monolayers floating over an aqueous solution of CdCl₂ inside an enclosed Langmuir-Blodgett set-up, through slow infusion of H₂S gas. X-ray diffraction spectra suggest an oriented growth of the crystallites. The particle sizes were found to increase with duration of exposure to the H₂S gas. Atomic force microscopy indicated that the particles were nearly circular pellets with uniform morphology throughout. In Raman spectra, the FWHM of the LO phonon was found to be large (≈20 cm^-1) for all the films grown with different exposure times in H₂S gas, and was found to reduce to 8 cm^-1 after annealing a typical sample at 500 °C for 45 min. Received: 30 September 1998 / Accepted: 29 March 1999 / Published online: 11 August 1999     

57Fe-Mössbauer study of electrically conducting barium iron vanadate glass after heat treatment

Local structure and thermal durability of semiconducting xBaO·(90?? x)V₂O₅ · 10Fe₂O₃ glasses (x = 20, 30 and 40), NTA glass ^TM, before and after isothermal annealing were investigated by ⁵⁷Fe-Mössbauer spectroscopy and differential thermal analysis (DTA). An identical isomer shift ( $\mathit{\delta}$ ) of 0.39 ± 0.01 mm s^???1 and a systematic increase in the quadrupole splitting (Δ) were observed from 0.70 ± 0.02 to 0.80 ± 0.02 mm s^???1 with an increasing BaO content, showing an increase in the local distortion of Fe^IIIO₄ tetrahedra. From the slope of the straight line in the T _g–Δ plot of NTA glass ^TM, it proved that Fe^III plays a role of network former. Large Debye temperature (Θ _D) values of 1000 and 486 K were respectively obtained for 20BaO · 70V₂O₅ · 10Fe₂O₃ glass before and after isothermal annealing at 400°C for 60 min, respectively. This result also suggests that Fe^III atoms constitute the glass network composed of tetrahedral FeO₄, tetrahedral VO₄ and pyramidal VO₅ units. The electric conductivity of 20BaO · 70V₂O₅ · 10Fe₂O₃ glass increased from 1.6 × 10^???5 to 5.8 × 10^???2 S cm^???1 after isothermal annealing at 450°C for 2,000 min. These results suggest that the drastic increase in the electric conductivity caused by heat treatment is closely related to the structural relaxation of the glass network 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.     

Volume and surface oxidation of basalt

Natural, Fe²⁺-rich basalt glass (quenched lava) was heat treated as glass pieces and glass powder in air, in 6.0 Ar and in a 9×10^?6 mbar vacuum below temperatures of significant crystallization to access volume and surface oxidation by ⁵⁷Fe Mössbauer spectroscopy. While no oxidation occurs upon heating in vacuum, the amount of Fe³⁺ formed in powder (surface oxidation) is about 10 times higher than in pieces (volume oxidation), and surface oxidation is of the same order in air and Ar. This effect is assigned to chemisorption of water or CO₂. Crystalline basalt, investigated by wet chemistry, includes five glass pieces treated above T of crystallization in air and in 6.0 Ar, and three lava samples of increasing depth up to 9 cm of lava lobes. The high Fe₂O₃ of all these crystalline samples is explained as a stabilization of Fe³⁺ due to the change of the local electronic environment in the course of crystallization; volume oxidation therefore appears to be independent on the environmental atmosphere.     

Growth of nanostructures of Zn/ZnO by thermal evaporation and their application for room-temperature sensing of H<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript>S gas

ZnO micro- and nanostructures were prepared by thermal evaporation of Zn and a mixture of ZnO with graphite. On heating Zn powder in a quartz tube at temperatures between 600 °C to 800 °C, radial growth of nanowires was observed on the source. On increasing the temperature to 900 °C, various interesting micro- and nanostructures of Zn and ZnO were observed to have deposited all over the quartz tube. On the other hand, when ZnO was heated in the presence of graphite, predominant growth of ZnO nanotetrapods was observed. Nanowires and tetrapods of ZnO were characterized by photoluminescence measurements and were found to show significantly improved response for detection of H₂S gas at room temperature when compared with earlier studies. The response was seen to improve with increase in oxygen vacancies in the material. PACS 78.55.Et; 07.07.Df     

The optimal condition for H<Subscript>2</Subscript>TiO<Subscript>3</Subscript>–lithium adsorbent preparation and Li<Superscript>+</Superscript> adsorption confirmed by an orthogonal test design

An orthogonal test design was applied to confirm the optimum condition for H₂TiO₃–lithium adsorbent preparation and Li⁺ adsorption. Extraction and adsorption mechanism and cycle performance were studied. The verified optimal condition is confirmed as the Li⁺ concentration, adsorption temperature, molar ratio of Li/Ti, reaction, and pre-calcination temperature are 4.0 g L^?1, 60 °C, 2.2, and 650 and 25 °C, respectively. Under the optimal condition, the adsorptive capacity reaches 57.8 mg g^?1. Adsorptive capacity of the adsorbent maintains in 5 cycles, typically 25–30 mg g^?1.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.