Molecular material—{N(n-C4H9)4[Ni(II)0.5 Fe(II)0.5 Fe(III)(C2O4)3]}∞: Magnetic, Mössbauer and electrical conductivity studies

We have attempted to characterize the magnetic and electrical properties of a new mixed-metal molecular material {NBu₄[Ni(II)_0.5Fe(II)_0.5Fe(III)(ox)₃]}_N synthesized by the use of trioxalatoferrate as the building block. Mössbauer spectroscopy was utilized in order to understand local spin structures in this compound. The results indicate that the compound is a semiconducting ferrimagnet with T_N=30 K and room temperature conductivity of 6×10⁻¹⁵ Ω⁻¹ cm⁻¹ along with 1.8 eV activation energy under dark. The compound has no appreciable electrical response towards illumination.     

An experimental study on the effect of mesoporous silica addition on ion conductivity of poly(ethylene oxide) electrolytes

Solid polymer electrolyte (SPE) composites, which are composed of poly(ethylene oxide) (PEO), mesoporous silica (SBA-15), and lithium salt were prepared in order to investigate the influence of SBA-15 content on the ionic conductivity of the composites. The ionic conductivity of the SPE composites was monitored by frequency response analyzer (FRA), and the crystallinity of the SPE composites was evaluated by using XRD. As a result, the addition of SBA-15 to the polymer mixture inhibited the growth of PEO crystalline domain, due to the mesoporous structure of the SBA-15. Also, the PEO₁₆LiClO₄/SBA-15 composite electrolytes show an increased ion conductivity as a function of SBA-15 content up to 15 wt.%. These ion conductivity characteristics are dependent on crystallinity with SBA-15 content.     

57Fe Mössbauer studies of nickel hydride

Nickel loaded with hydrogen electrolytically or under high pressure was studied by⁵⁷Fe Mössbauer spectroscopy on dilute substitutional iron solutes. Experiments in external magnetic fields at 4.2 K show that Fe species in nickel hydride have magnetic moments between about 4.7 and 2.5 μ_B and saturation hyperfine fields between 24 and 17 T, depending on the number of nearest hydrogen neighbours. By quenching hydride samples from ambient to liquid nitrogen temperature, non-equilibrium hydrogen distributions in the vicinity of the iron can be frozen in. They relax towards equilibrium between 130 and 150 K within hours, permitting information on hydrogen jump rates to be obtained.     

Electrical conductivity in magnesium-doped Al2O3 crystals at moderate temperatures

Abstract

AC and DC electrical measurements between 273 and 800 K were used to characterize the electrical conductivity of Al₂O₃: Mg single crystals containing [Mg]⁰ centers. At low fields contacts are blocking. At high fields, electrical current flows steadily through the sample and the I–V characteristic corresponds to a directly biased barrier with a series resistance (bulk resistance). AC measurements yield values for the junction capacitance as well as for the sample resistance, and provide reproducible conductivity values. The conductivity varies linearly with the [Mg]⁰ concentration and a thermal activation energy of 0.67 eV was obtained, which agrees very well with the activation energy previously reported for the motion of free holes.     

Reduction of Se(VI) to Se(-II) by zerovalent iron nanoparticle suspensions

The reaction of selenate (Se(VI)) with zerovalent iron nanoparticles (nano Fe⁰) was studied using both conventional batch equilibrium and X-ray spectroscopic techniques. Nano Fe⁰ has a high uptake capacity for removal of dissolved Se(VI) reaching concentrations as high as 0.10 Se:Fe molar ratio in the solid product mixture. Kinetic studies of the Se(VI) uptake reaction in batch experiments showed an initial reaction rate (0–30 min) of 0.0364 min^?1 which was four times greater than conventional Fe⁰ powder. Analysis of the oxidation state of Se in the solid products by X-ray absorption near edge structure (XANES) spectroscopy showed evidence for the reduction of Se(VI) to insoluble selenide (Se(-II)) species. Structural analysis of the product by extended X-ray absorption fine structure (EXAFS) spectroscopy suggested that Se(-II) was associated with nano Fe⁰ oxidation products as a poorly ordered iron selenide (FeSe) compound. The fitted first shell Se–Fe interatomic distance of 2.402 (±0.004) Å matched closely with previous studies of the products of Se(IV)-treated Fe(II)-clays and zero-valent iron/iron carbide (Fe/Fe₃C). The poorly ordered FeSe product was associated with Fe⁰ corrosion product phases such as crystalline magnetite (Fe₃O₄) and Fe(III) oxyhydroxide. The results of this investigation suggest that nano Fe⁰ is a strong reducing agent capable of efficient reduction of soluble Se oxyanions to insoluble Se(-II).     

Adsorption of octadecyltrichlorosilane on mesoporous SBA-15

Adsorption of octadecyltrichlorosilane (OTS) on mesoporous SBA-15 has been studied by using Brunauer-Emmett-Teller (BET) surface area analysis, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermo-gravimetric analysis (TGA) techniques. BET surface area analysis shows decrease of surface area from 930 to 416 m²/g after OTS adsorption. SEM pictures show close attachment of SBA-15 particles. EDAX measurements show increase of carbon weight percentage and decrease of oxygen and silicon weight percentage. XPS results closely support EDAX analysis. FTIR spectra shows presence of methyl (-CH₃) and methylene (-CH₂) bands and oriented OTS monolayer on SBA-15. Thermo-gravimetric analysis shows that the OTS adsorbed on SBA-15 are stable up to a temperature of 230 °C and that the OTS monolayers decompose between 230 and 400 °C.     

Influence of polarization and iron content on the transport properties of praseodymium–barium manganite

Polarization and iron effects on the electrical properties of Pr_0.67Ba_0.33Mn_1−xFe_xO₃ have been studied using impedance measurements. When iron is introduced, the insulator–metal transition (MI), observed in free compound, disappears and destroying such transition needs an iron concentration less than 5%. We also found that electrical conductance decreases when increasing Fe content. Such results are attributed to the decrease of Mn³⁺/Mn⁴⁺ ratio. Also, they are ascribed to the high probability of encountering Fe³⁺–O–Fe³⁺ and Mn³⁺–O–Fe³⁺ interactions, which greatly weakens the influence of Mn³⁺–O–Mn⁴⁺ interactions. The AC conductivity studies indicate that different types of hopping are involved. The contribution of hopping mechanism is confirmed by the temperature dependence of the frequency exponent ‘s’. Conductivity analysis shows that small polaron hopping (SPH) and variable range hopping (VRH) models are present in the conduction process. For small iron concentrations (x<0.1), we found that activation energy (E_a) does not changes significantly. Such result is in good agreement with the literature. But, for high iron concentrations (x>0.1), we found that E_a depend strongly in Fe content. We also found in this work that DC-bias does not affect the conduction process but proves its thermal activation. The variation of the conductance with polarization is a proof of an electro-resistance effect.     

A study on ac and dc conductivity characteristics of Y-doped BaCeO3 modified by Ar+ ion beam

The effects of surface modification on electrical characteristics in bulk, grain boundary and interface (electrolyte/electrode) of BaCe_0.9Y_0.1O_3-δ were investigated. The surface modification was performed by means of two processes: specimen was firstly irradiated by 10 keV Ar⁺ ion with dose of 1 × 10¹⁸ ions/cm² and then exposed to air. The modified surface was investigated by elastic recoil detection analysis (ERDA) for quantitative analysis of hydrogen concentration on the surface and alternating current (AC) and direct current (DC) conductivity measurements, respectively. The ERDA results showed that hydrogen concentration and reaction rate on the modified surface increased. The increase of hydrogen concentration was explained in terms of the increase of proton due to interaction between oxygen vacancy formed by modification and H₂O. In AC and DC electrical conductivity measurements, it concluded that the proton and electronic carrier generated on the surface by modification attributed to the increase of bulk, grain boundary and interface conductivity.     

Effect of Ar+ irradiation on the electrical conductivity of BaCe0.9Y0.1O3−δ

The effects of 10 keV Ar⁺ ion irradiation on the electrical characteristics of BaCe_0.9Y_0.1O_2.95 subject to fluences of 0, 1.0 × 10¹⁷, 5.0 × 10¹⁷ and 1.0 × 10¹⁸ ions/cm² at room temperature, has been investigated using elastic recoil detection analysis (ERDA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and alternating current (AC) impedance measurements. It was confirmed from the ERDA results that the hydrogen concentration near the surface increased with increase of Ar⁺ ion fluence. This increase may be associated with the increasing quantities of hydrogen generated by interaction between oxygen vacancies, formed by irradiation, and H₂O from exposure to air. SEM images showed clearly that the number of surface defects due to modification increased with increasing fluence. In addition, the size of the defects showed a tendency to increase with increasing fluence. From the results of XPS analyses, providing information on the electronic states on the surface, it was evident that with increase in the Ar⁺ ion fluence, the quantity of excess oxygen, such as hydroxide, increased in the oxygen 1s XPS spectrum. In addition, it was indirectly found, from decomposition of the Ce 3d, spectrum that the concentration of oxygen vacancies increased with fluence, since the percentage of Ce³⁺ also increased. Accordingly, the surface modification led to the formation of more oxygen vacancies and a greater hydrogen concentration on the surface, since the H₂O interacted with some of them. From the results of the DC conductivity and AC impedance measurements, the proton conductivity was shown to predominate over the temperature range from 473 K to 823 K. It was concluded that the increase in these protons and vacancies generated from surface modification contributed to the increase of proton conductivity.     

Investigation of the hydrides of Ni0.70Cu0.30 by57Fe Mössbauer spectroscopy and magnetization measurements

Hydrides of Ni_0.70Cu_0.30 prepared both electrolytically and under high pressures of hydrogen gas were studied by Mössbauer spectroscopy on dilute⁵⁷Fe probes and by magnetization measurements. At hydrogen-to-metal ratios abovex≈0.3 no ferromagnetism is observed down to 4.2 K. The dependence of the mean change of the isomer shift on the hydrogen content of the samples reveals a repulsive interaction between the hydrogen interstitials and the iron probes. The effect of this interaction is, however, less pronounced than for⁵⁷Fe in the hydrides of pure nickel. This difference can be attributed to a competition of the repulsive Fe?H and Cu?H interactions.     

The superexchange interactions in mixed Co-Fe ludwigite

The crystal structure, cation distribution and exchange interactions in the Co_2.25Fe_0.75O₂BO₃ ludwigite have been explored through X-ray diffraction, electrical resistivity, ac-susceptibility and Mossbauer effect measurements. The crystal data have shown that iron atoms occupy the most symmetric crystallographic sites Fe4 and Fe2. The complex magnetic behavior with two magnetic transitions near 70 and 115 K at low temperatures was found. The Mossbauer data have displayed the trivalent iron states only. The values of superexchange energies have been estimated for Co₃O₂BO₃ and Co_2.25Fe_0.75O₂BO₃ yielding a significant role of frustrations in the ludwigite magnetic system. Variable range Mott hopping conductivity law was proved to be valid in the wide temperature region, pointing out a localized character of charge carriers rather than collective.     

Study of iron implanted MgO crystals by low-energy electron induced X-ray spectroscopy

Magnesium oxide crystals implanted with Fe⁺ ions have been studied by means of Low-Energy-Electron-Induced X-ray Spectroscopy. All the implantations were carried out with 100 or 150 keV ion energy, at doses in the range from 10¹⁵ to 10¹⁷ ions cm^?2. The structure of the Fe L_II, L_III X-ray emission bands provides information about the iron chemical state. Fe L_II/L_III band intensity ratio measurements have been performed with a 3 keV electron excitation in order to investigate the whole implanted layer. In addition, by using a filtered Fourier transform technique on observed spectra, some modifications in the oxygen K emission band can be observed in implanted MgO crystals after thermal annealings in air. The oxygen spectrum fine structure suggests that the MgO matrix, partially destroyed by iron implantation, is restored after high temperature treatments. All the implantation, is restored after high temperature treatments. All the results are discussed on the basis of previous Mössbauer Spectroscopy studies and ion channeling investigations.     

CO2 adsorption on branched polyethyleneimine-impregnated mesoporous silica SBA-15

Adsorption of pure CO₂ on SBA-15 impregnated with branched polyethyleneimine (PEI) has been studied. Materials were prepared by impregnating the pore surface of SBA-15 mesoporous silica with different amounts of branched PEI (10, 30, 50 and 70 wt%). Textural properties, elemental analysis and low angle XRD measurements of the prepared samples showed a progressive pore filling of SBA-15 as PEI loading was increased. Pure CO₂ adsorption isotherms on these modified SBA-15 materials were obtained at 45 °C, showing high adsorption efficiency for CO₂ removal at 1 bar. Chemisorption of CO₂ on amino sites of the modified SBA-15 seems to be the main adsorption mechanism. PEI content of impregnated SBA-15 influences the adsorption capacity of the material, being a relevant variable for CO₂ removal by adsorption. Temperature effect on adsorption was also studied in the range 25-75 °C, showing that temperature strongly influences CO₂ adsorption capacity. Adsorption capacity was also tested after regeneration of the PEI-impregnated SBA-15 materials. Our results show that these branched PEI-impregnated materials are very efficient even at low pressure and after several adsorption-regeneration cycles.     

Role of precursor alloy phases and intermediate oxides in the preparation of Raney and Urushibara iron

⁵⁷Fe Mössbauer spectroscopy and scanning electron microscopy measurements of precursor phases formed during catalyst preparation and of the catalysts, themselves, demonstrate that the preparation of Raney iron from iron aluminum alloys involves the formation of Fe(OH)₂ and Fe₃O₄ as intermediate phases. The metallic Fe is formed from subsequent reduction of Fe₃O₄ by hydrogen generated by the oxidation of aluminum metal by hydroxide ions. Precursors to Urushibara iron U?Fe (III) are found to consist of Fe?Zn alloys when Zn is used as a reductant and of epitaxial deposits of Fe on aluminum when Al is the reductant. The material resulting from the reduction of the iron salt by aluminum is not a hydrogenation catalyst; the absence of catalytic activity is related to the absence of any alloying of the iron and aluminum. A consideration of the preparation of Raney iron, Urushibara iron, ammonia synthesis and Fischer-Tropsch catalysts leads to the conclusions that catalytic activity is highly correlated to the existence of intermediate mixed-crystals phases and the presence of intimate mixtures of at least two phases in the final catalyst.     

Developing a novel fluorescence chemosensor by self-assembly of Bis-Schiff base within the channel of mesoporous SBA-15 for sensitive detecting of Hg ions

A novel fluorescence chemosensor for Hg²⁺ ion has been developed by the assembly of fluorescence Bis-Schiff base PMBA within the channels of CPTES-modified SBA-15. The ordered porous structure of SBA-15 is still retained on the hybrid chemosensor material PMBA-SBA. A remarkable fluorescence quenching of PMBA-SBA by Hg²⁺ ion was attributed to heavy atom effect of Hg²⁺ ion. The linear detecting range of the hybrid mesoporous chemosensor for Hg²⁺ ion is 2-15 μM and the lowest detection limit is 0.6 μM in ethanol/water (9:1, v/v) solution.     

Electrical and complex dielectric behaviour of composite polymer electrolyte based on PEO,alumina and tetrapropylammonium iodide

In this study, the electrical, dielectric and morphological analysis of composite solid polymer electrolytes containing polyethylene oxide, alumina nano-fillers and tetrapropylammonium iodide are conducted. The temperature dependence of conductivity shows activation energy of 0.23, 0.20 and 0.29 eV for electrolytes containing 0, 5 and 15 wt.% alumina, respectively, when data fitted to the Arrhenius equation. These activation energy values are in good agreement with those determined from dielectric measurements. The result confirms the fact that conductivity is activated by both the mobility and the charge carrier density. The conductivity isotherms demonstrated the existence of two peaks, at 5 and 15 wt.% Al₂O₃ composition. The highest conductivity values of 2.4 × 10^?4, 3.3 × 10^?4 and 4.2 × 10^?4 S cm^?1 are obtained for the sample with 5 wt.% Al₂O₃ at 0, 12 and 24 °C, respectively, suggesting an enhancement of conductivity compared with that of alumina free samples.     

In-situ control of different oxygen fugacity experimental study on the electrical conductivity of lherzolite at high temperature and high pressure

At pressure 1.0-4.0 GPa and temperature 1073-1423 K and under the control of oxygen fugacity (Mo+MoO₂, Fe+FeO and Ni+NiO), a YJ-3000t multi-anvil solid high-temperature and high-pressure apparatus and Solartron-1260 impedance/Gain-Phase analyzer were employed to analyze the electrical conductivity of lherzolite. The experimental results showed that: (1) within the range of the selected frequencies (10³-10⁶ Hz), either as viewed from the relationship between the real or imaginary part of complex impedance and the frequency, or from the relationship between modulus, phase angle and frequency, it can be seen clearly that the complex impedance has a strong dependence on frequency; (2) with the rise of temperature (T), the electrical conductivity (σ) increased, and Lg σ and 1/T follows the Arrhenius relationship; (3) with the rise of pressure, the electrical conductivity decreased, and activation enthalpy and temperature-independent pre-exponential factor decreased as well. And the activation energy and activation bulk volume of the main charge carrier in the lherzolite have been obtained for the first time, which are 1.68±0.02 eV and 0.04±0.01 cm³/mol, respectively; (4) under the given pressure and temperature, the electrical conductivity tends to increase with increasing oxygen fugacity, and under the given pressure, the activation enthalpy and pre-exponential factor tend to decrease with the rise of oxygen fugacity; (5) at 2.0 GPa and the control of the three solid buffers, Mo+MoO₂, Fe+FeO and Ni+NiO, the exponential factors of electrical conductivity variation range with oxygen fugacity are , and the theoretical model for the relationship between the electrical conductivity of lherzolite and the oxygen fugacity under high pressure has been established for the first time; (6) the electrical conduction mechanism of small polarons provides a reasonable explanation to the variation of conductivity of lherzolite with oxygen fugacity.     

Investigations on Fe doped polyvinyl alcohol films with and without gamma (γ)-irradiation

This paper deals with the preparation of pure and ferric chloride (FeCl₃) doped polyvinyl alcohol (PVA) films by solution casting method. Optical and electrical properties were systematically investigated. We have found the decrease in optical band gap energy of PVA films on doping FeCl₃. The optical band gap energy values in the present work are found to be 3.10 eV for pure PVA, 2 eV for PVA:Fe³⁺ (5 mol%), 1.91 eV for PVA:Fe³⁺(15 mol%) and 1.8 eV for PVA:Fe³⁺(25 mol%). Direct current electrical conductivity (σ) of pure, FeCl₃ doped PVA films in the temperature range 70-127 °C has been studied. At 387 K dc electrical conductivity of pure PVA film is 5.5795 μ Ω⁻¹ cm⁻¹, PVA:Fe³⁺ (5 mol%) film is 10.0936 μ Ω⁻¹ cm⁻¹ and γ-Irradiated PVA:Fe³⁺ (5 mol%) film for 900 CGY/min is 22.1950 μ Ω⁻¹ cm⁻¹. The result reveals the enhancement of the electrical conductivity with γ-irradiation. FT-IR study signifies the intermolecular hydrogen bonding between Fe³⁺ ions of FeCl₃ with OH group of PVA.     

Improving the electrical conductivity of CuCrO2 thin film by N doping

N-doped CuCrO₂ thin films were prepared by using radio frequency magnetron sputtering technique. The XRD and XPS measurements were used to confirm the existence of the N acceptors in CuCrO₂ thin films. Hall measurements show the p-type conduction for all films. The electrical conductivity increases rapidly with the increase in N doping concentration, and the maximum of the electrical conductivity of 17 S cm⁻¹ is achieved for the film deposited with 30 vol.% N₂O, which is about three orders of magnitude higher than that of the undoped CuCrO₂ thin film. Upon increasing the doping concentrations the band gaps of N-doped CuCrO₂ thin films increase due to the Burstein-Moss shift.     

CP MAS Kinetics Study of Ionic Liquids Confined in Mesoporous Silica: Convergence of Non-Classical and Classical Spin Coupling Models

The high data point density measurements of ¹H→¹¹B cross-polarization (CP) kinetics upon magic-angle spinning (MAS) of [bmim][BF₄] confined in mesoporous SBA-15 and MCM-41 were carried out. The complex shaped ¹¹B CP MAS signals were observed in both silica and decomposed into two Lorentz components. This points towards the possibility of bimodal distribution of [bmim][BF₄] in the studied confinements. The convergence of classical and non-classical spin coupling models was deduced processing CP kinetic curves. A good fit of the theoretical curves to the experimental data was achieved using both models without any non-random deviations between theory and experiment to appear. The convergence of spin coupling models was discussed in terms of relatively high mobility of BF₄ ^? anion respect to the cation and the dynamics of anions in pores. These factors delete the borders between spin clusters. The spin diffusion along the pore surfaces in MCM-41 is more than twice faster than in SBA-15.