Preparation of core-shell magnetic Fe3O4@SiO2-dithiocarbamate nanoparticle and its application for the Ni2+, Cu2+ removal

A typical superparamagnetic nanoparticles-based dithiocarbamate absorbent (Fe₃O₄@SiO₂-DTC) with core-shell structure was applied for aqueous solution heavy metal ions Ni²⁺, Cu²⁺ removal.     

Redox behavior and transport properties of La0.5−2xCexSr0.5+xFeO3−δ and La0.5−2ySr0.5+2yFe1−yNbyO3−δ perovskites

The effects of doping the mixed-conducting (La,Sr)FeO_3−δ system with Ce and Nb have been examined for the solid-solution series, La_0.5−2xCe_xSr_0.5+xFeO_3−δ (x = 0–0.20) and La_0.5−2ySr_0.5+2yFe_1−yNb_yO_3−δ (y = 0.05–0.10). Mössbauer spectroscopy at 4.1 and 297 K showed that Ce⁴⁺ and Nb⁵⁺ incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for La_0.3Sr_0.7Fe_0.90Nb_0.10O_3−δ at 923–1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10⁻⁵–0.5 atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe⁴⁺ concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 × 10⁻³ for La_0.3Sr_0.7Fe_0.9Nb_0.1O_3−δ cf. 1.3 × 10⁻³ for La_0.5Sr_0.5FeO_3−δ at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0–21.2) × 10⁻⁶ K⁻¹ at 780–1080 K.     

Fe-doped SnO2 transparent semi-conducting thin films deposited by spray pyrolysis technique: Thermoelectric and p-type conductivity properties

In this paper, we report structural, electrical, optical, and especially thermoelectrical characterization of iron (Fe) doped tin oxide films, which have been deposited by spray pyrolysis technique. The doping level has changed from 0 to 10 wt% in solution ([Fe]/[Sn] = 0–40 at% in solution). The thermoelectric response versus temperature difference has exhibited a nonlinear behavior, and the Seebeck coefficient has been calculated from its slope in temperature range of 300–500 K. The Hall effect and thermoelectric measurements have shown p-type conductivity in SnO₂:Fe films with [Fe]/[Sn] ≥ 7.8 at%. In doping levels lower than 7.8 at%, SnO₂:Fe films have been n-type with a negative thermoelectric coefficient. The Seebeck coefficient for SnO₂:Fe films with 7.8 at% doping level has been obtained to be as high as +1850 μV/K. The analysis of as-deposited samples with thicknesses ～350 nm by X-ray diffraction (XRD) and scanning electron microscopy (SEM) has shown polycrystalline structure with clear characteristic peak of SnO₂ cassiterite phase in all films. The optical transparency (T%) of SnO₂:Fe films in visible spectra decreases from 90% to 75% and electrical resistivity (ρ) increases from 1.2 × 10^?2 to 3 × 10³ Ω cm for Fe-doping in the range 0–40 at%.     

Magnetically recyclable Schiff-based palladium nanocatalyst [Fe3O4@SiNSB-Pd] and its catalytic applications in Heck reaction

A magnetically separable palladium nanocatalyst has been synthesized through the immobilization of palladium onto 3-aminopropylphenanthroline Schiff based functionalized silica coated superparamagnetic Fe₃O₄ nanoparticles. The nanocatalyst (Fe₃O₄@SiNSB-Pd) was fully characterized using several spectroscopic techniques, such as FT-IR, HR-SEM, TEM, XRD, ICP, and XPS. The microscopic image of Fe₃O₄ showed spherical shape morphology and had an average size of 150 nm. The Pd-nanoparticles exhibited an average size 3.5 ± 0.6 nm. The successful functionalization of Fe₃O₄@SiNSB-Pd was identified by FT-IR spectroscopy and the appearance of palladium species in Fe₃O₄@SiNSB-Pd was confirmed by XRD analysis. While XPS has been utilized for the determination of the chemical oxidation state of palladium species in Fe₃O₄@SiNSB-Pd. Several activated and deactivated arene halides and olefines were employed for Mizoroki-Heck cross-coupling reactions in the presence of Fe₃O₄@SiNSB-Pd, each of which produced the respective cross-coupling products with excellent yields. The Fe₃O₄@SiNSB-Pd shows good reactivity and reusability for up to seven consecutive cycles.     

Synthesis and structural mechanisms of the 2201-type ferrites and polytypes: Fe2(Sr2 − xAx)FeO6.5 − δ/2 (A = Ba,La, Tl,Pb and Bi)

The Fe₂(Sr_2 ? xA_x)FeO_6.5 ? δ/2 systems have been investigated, by doping the iron rich 2201-type parent structure with Ba²⁺, La³⁺ and 5d¹⁰ post-transition cations. The syntheses have been carried out up to the limit of the 2201-type solid solutions, in order to test the role of the double iron layer Fe₂O_2.5 ? δ/2. The localisation of the charge carriers in these compounds is consistent with their strong antiferro-magnetism. The investigation was then carried out in the transition part of the diagram up to the formation of stable phases. The study of structural mechanisms was carried using high resolution electron microscopy (transmission and scanning transmission), electron diffraction and energy dispersive spectroscopy. Different non-stoichiometry mechanisms are observed, depending on the electronic structure and chemical properties of the doping elements. The specific behavior of the modulated double iron layer is discussed.     

Role of core diameter and silica content in photocatalytic activity of TiO2/SiO2/Fe3O4 composite

Magnetically separable TiO₂/SiO₂/Fe₃O₄ composites of different core (Fe₃O₄) diameters and silica contents have been prepared by sol–gel technique for both silica and titania coatings. Energy dispersive X-ray fluorescence (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), BET surface area analysis and scanning electron microscope (SEM) have been used for characterization of prepared samples. Photocatalytic activity of the prepared samples has been investigated by photodegradation of methyl orange. Obtained results have shown that 25–45 μm core diameter exhibits the maximum activity since it possesses a convenient surface area and light transmittance. Silica content has a significant effect on the activity of composite. Silica content of more than 10 wt% has reduced the catalyst activity because of the increase in particle diameter and reduction of surface area.     

Structures,thermal expansion properties and phase transitions of ErxFe2−x(MoO4)3 (0.0 ≤ x ≤ 2.0)

Structures, thermal expansion properties and phase transitions of Er_xFe_2−x(MoO₄)₃ (0.0 ≤ x ≤ 2.0) have been investigated by X-ray diffraction and differential thermal analysis. The partial substitution of Er³⁺ for Fe³⁺ induces pronounced decreases in the phase transition temperature from monoclinic to orthorhombic structure. Rietveld analysis of the XRD data shows that both the monoclinic and orthorhombic Fe₂(MoO₄)₃, as well as the orthorhombic Er_xFe_2−x(MoO₄)₃ (x ≤ 0.8) have positive thermal expansion coefficients. However, the linear thermal expansion coefficients of Er_xFe_2−x(MoO₄)₃ (x = 0.6–2.0) decrease with increasing content of Er³⁺ and for x ≥ 1.0, compounds Er_xFe_2−x(MoO₄)₃ show negative thermal expansion properties. Attempts for making zero thermal expansion coefficient materials result in that very low negative thermal expansion coefficient of −0.60 × 10⁻⁶/°C in Er_1.0Fe_1.0(MoO₄)₃ is observed in the temperature range of 180–400 °C, and zero thermal expansion is observed in Er_0.8Fe_1.2(MoO₄)₃ in the temperature range of 350–450 °C. In addition, anisotropic thermal expansions are found for all the orthorhombic Er_xFe_2−x(MoO₄)₃ compounds, with negative thermal expansion coefficients along the a axes.     

Impact of Fe3+ on UV absorption of K2Al2B2O7 crystals

K₂Al₂B₂O₇ (KABO) is a new nonlinear optical crystal capable of laser harmonic generation in the UV range. However, abnormal UV absorption prevents its application in effectively generating UV light with wavelength shorter than 300 nm. The transmittance spectra of the grown crystals show distinct absorption bands at 216 nm and 264 nm. It is observed that the UV absorption is strongly correlated with iron impurity at a parts per million (ppm) level. Furthermore, electron paramagnetic resonance (EPR) spectra of the absorbing crystals show a strong signal at g = 2.00 position corresponding to a Fe³⁺ center. A new crystal growth method which reduces the iron content has been proposed and results show that the new KABO crystal is free from the Fe³⁺ UV absorptions.     

Structure and oxygen storage capacity of Pr/Nd doped CeO2–ZrO2 mixed oxides

Binary Ce–Zr (CZ), trinary Ce–Zr–Pr (CZP), Ce–Zr–Nd (CZN) mixed oxides were prepared by coprecipitation. The structural and textural properties were characterized by the X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) method, Raman and X-ray absorption near-edge spectra (XANES) techniques, while the oxygen storage capacity (OSC) was evaluated under both dynamic and static conditions at 500 °C. The doping of Pr or Nd cations causes the lattice deformation of the tetragonal Zr-rich mixed oxides to form a pseudocubic structure and prevents the phase demixing after calcination in flowing steam/air at 1050 °C for 5 h. After the hydrothermal ageing treatment, the doped samples show higher BET surface areas and better oxygen mobility. Pr exists mainly in the form of trivalent cations in the aged CZP and functions primarily as the doping element with large ionic radius instead of redox couple Pr³⁺/Pr⁴⁺, which may introduce more Ce³⁺ species and hereby more lattice defects. Among the aged samples, CZP shows the best oxygen storage capacity and the fastest oxygen release rate.     

Effect of bication (Cu-Cr) substitution on the structure and electrochemical performance of LiMn2O4 spinel cathodes at low and high current rates

This report describes the detailed structural and electrochemical characterization of a series of low content (0.01 to 0.05) Cu-Cr bi-metal doped LiMn₂O₄ cathode material synthesized by sol–gel method. The structural and morphological features were described using XRD, SEM, TEM, EDAX and FTIR techniques. The electron transfer and its feasibility were discussed through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The charge–discharge studies were performed to evaluate the capacity fading and rate capability. It was found that the electrochemical performance is very much dependent on the amount of Cu-Cr bi-metal doping and interestingly decreased the capacity fading with high cycleability. The sample with the least amount of dopants (i.e., LiCu_0.01Cr_0.01Mn_1.98O₄) demonstrated much improved capacity, cycleability and high rate capability. The LiCu_0.01Cr_0.01Mn_1.98O₄ cathode exhibited a discharge capacity of 112 mA h g^?1 at very first cycle and retained 93 mA h g^?1 after 100 cycles at a C rate of 0.3. Further, the same material at very high current density (5 C) retained 83% of the initial discharge capacity. The Cu-Cr doping stabilized the spinel structure by suppressing the Jahn-Teller distortion effect and Mn dissolution and the resultant material showed the workability of the cathodes for devices which work at substantially high C-rate of 5C.     

Recyclable Fenton-like catalyst based on zeolite Y supported ultrafine,highly-dispersed Fe2O3 nanoparticles for removal of organics under mild conditions

The active Fenton-like catalyst, obtained by highly dispersed Fe₂O₃ nanoparticles in size of 5 nm on the surface of zeolite Y, shows the excellent degradation efficiency to phenol higher than 90% under the mild conditions of room temperature and neutral solution, and the catalyst can be easily recovered with stable catalytic activity for 8 cycles.     

Thermal decomposition pathway of undoped and doped zinc layered gallate nanohybrid with Fe3+, Co2+ and Ni2+ to produce mesoporous and high pore volume carbon material

A series of brucite-like materials, undoped and doped zinc layered hydroxide nitrate with 2% (molar) Fe³⁺, Co²⁺ and Ni²⁺ were synthesized. Organic–inorganic nanohybrid material with gallate anion as a guest, and zinc hydroxide nitrate, as an inorganic layered host was prepared by the ion-exchange method. The nanohybrid materials were heat-treated at various temperatures, 400–700 °C. X-ray diffraction, thermal analysis and also Fourier transform infrared results showed that incorporation of the doping agents within the zinc layered hydroxide salt layers has enhanced the heat-resistivity of the nanohybrid materials in the thermal decomposition pathway. Porous carbon materials can be obtained from the heat-treating the nanohybrids at 600 and 700 °C. Calcination of the nanohybrids at 700 °C under nitrogen atmosphere produces mesoporous and high pore volume carbon materials.     

Mössbauer spectroscopic study of photo-sensitive organic–inorganic hybrid system, (SP)[Fe(II)Fe(III)(dto)3](dto = C2O2S2, SP = spiropyran)

A photo-sensitive organic–inorganic hybrid system (SP)[Fe^IIFe^III(dto)₃] (SP = spiropyran, dto = C₂O₂S₂), has recently been developed, where the photo-isomerization of the intercalated spiropyran in solid state triggers the change of the magnetic properties, including the ferromagnetic transition temperature from 5 to 22 K. We performed ⁵⁷Fe Mössbauer measurement in order to probe the microscopic states of iron ions in (SP)[Fe^IIFe^III(dto)₃] and have investigated the photo-induced effect on them. The sample without UV-irradiation shows the charge transfer phase transition between 200 and 70 K and the higher and lower temperature phases coexist below 70 K, whereas the UV-irradiated sample does not undergo the charge transfer phase transition and the higher temperature phase is stable between 200 and 6 K.     

Iron (III) nanocomposites for enzyme-less biomimetic cathode: A promising material for use in biofuel cells

In this paper, we discuss the synthesis and electrochemical properties of a new material based on iron oxide nanoparticles stabilized with poly(diallyldimethylammonium chloride) (PDAC); this material can be used as a biomimetic cathode material for the reduction of H₂O₂ in biofuel cells. A metastable phase of iron oxide and iron hydroxide nanoparticles (PDAC–FeOOH/Fe₂O₃-NPs) was synthesized through a single procedure. On the basis of the Stokes–Einstein equation, colloidal particles (diameter: 20 nm) diffused at a considerably slow rate (D = 0.9 × 10^? 11 m s^? 1) as compared to conventional molecular redox systems. The quasi-reversible electrochemical process was attributed to the oxidation and reduction of Fe³⁺/Fe²⁺ from PDAC–FeOOH/Fe₂O₃-NPs; in a manner similar to redox enzymes, it acted as a pseudo-prosthetic group. Further, PDAC–FeOOH/Fe₂O₃-NPs was observed to have high electrocatalytic activity for H₂O₂ reduction along with a significant overpotential shift, ΔE = 0.68 V from ? 0.29 to 0.39 V, in the presence and absence of PDAC–FeOOH/Fe₂O₃-NPs. The abovementioned iron oxide nanoparticles are very promising as candidates for further research on biomimetic biofuel cells, suggesting two applications: the preparation of modified electrodes for direct use as cathodes and use as a supporting electrolyte together with H₂O₂.     

Synthesis and characterization of Fe3O4@SiO2@poly-l-alanine,peptide brush–magnetic microspheres through NCA chemistry for drug delivery and enrichment of BSA

A novel Fe₃O₄@SiO₂@poly-l-alanine peptide brush–magnetic microsphere (PBMMs) was synthesized from amine-functionalized Fe₃O₄ through the surface-initiated polymerization of N-carboxyanhydrides. Two materials with different peptide lengths were obtained from different amounts of N-carboxyanhydrides. These materials were characterized by Fourier transform infrared, transmission electron microscopy, large-angle powder X-ray diffraction, vibrating sample magnetometer and elemental analysis. Furthermore, the loading and release behavior of ibuprofen and the enrichment of bovine serum albumin on the two materials were investigated and it was shown that the PBMMs have a maximum uptake amount of ibuprofen of 40.3 mg g⁻¹, and an enrichment of bovine serum albumin of 20.9 mg g⁻¹. These materials are promising candidates for targeted drug delivery and protein enrichment.     

Fabrication and properties of Mn0.5Zn0.5Fe2O4 nanofibers

Zn-doped α-FeOOH nanofiber was synthesized by coprecipitation method. Then the α-FeOOH was enwraped by the complex of the Mn²⁺ and citric acid. The morphology of α-FeOOH did not transform after the calcination process and Mn_0.5Zn_0.5Fe₂O₄ nanofiber was successfully prepared. The phase, morphology, particle diameter and the magnetic properties of samples were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The results indicated that Mn_0.5Zn_0.5Fe₂O₄ nanofibers with an aspect ratio over 40 and a diameter of 20 nm were prepared. Compared with the amorphous Mn_0.5Zn_0.5Fe₂O₄, the anisotropy of the Mn_0.5Zn_0.5Fe₂O₄ nanofiber increased, resulting in the higher coercivity and magnetization of the obtained sample. With an increase in the calcination temperature, the diameter and the saturation magnetization of the sample increased, while the aspect ratio and coercivity decreased. The coercivity of the sample obtained at 700 °C was maximal (up to 185.4 Oe). The saturation magnetization of the sample obtained at 900 °C was maximal (up to 65.3 emu/g). The use of citric acid method prevented the presence of Mn(OH)₂, resulting in the decrease of the calcination temperature.     

Preparation and characterization of NiO(core)/Fe2O3(shell) composite particles

A novel hydrothermal coating process has been developed to deposit amorphous Ni(OH)₂·H₂O over octahedral α-Fe₂O₃ particles by treating aqueous dispersion of the preformed cores in Ni(NO₃)₂/CH₃COONa solution. NiO_(core)/Fe₂O_3(shell) composite particles were prepared by air sintering of the Ni(OH)₂·H₂O_(shell)/Fe₂O_3(core) particles at 200–500°C for 1–6 h. The changes of morphology, structure and weight of the hydrothermal and sintering products were studied by means of TEM, XRD, XPS, TG and IR analyzers. The nucleation and growth model was suggested for the non-isothermal decomposition of Ni(OH)₂·H₂O coatings and the kinetic equation was derived from the non-linear regression of the TG data. The activation in the thermal-decomposition process is 73.8 kJ mol⁻¹ and the pre-exponential factor is 1.95×10⁴ s⁻¹.     

Some aspects of metal-support strong interactions in Rh/Al2O3 catalyst under oxidising and reducing conditions

The aim of the Letter is to elucidate the nature of metal-support interaction in the 2 wt% Rh/Al₂O₃ catalyst obtained by annealing Rh–O–Al xerogel at 1113 K in air.XPS, HRTEM, and XRD results reveal that during the Rh–O–Al xerogel annealing in air, rhodium incorporates into forming alumina, which results mostly in Rh⁴⁺/δ-Al₂O₃ solid solution formation.However, in the course of the catalyst reduction at 773 with H₂ and at 823 K with CH₄ the Rh⁴⁺/δ-Al₂O₃ solid solution transforms into Rh–Al alloy. The islands of rhodium form on the surface of the Rh–Al alloy nanocrystallites if the reduction is slow enough.     

Synthesis,physico-chemical and spectral investigations of novel homo-bimetallic mixed-ligand complexes: 57Fe Mössbauer parameters of [Fe2(imda)2(H2O)3Cl]

The newly prepared homo-bimetallic complexes [M₂(imda)₂(H₂O)₄], [M₂(imda)₂(Bipy)₂] (M = Co, Ni or Cu) and [Fe₂(imda)₂(H₂O)₃Cl] (H₂imda = iminodiacetic acid and Bipy = 2,2′-bipyridine) have been studied employing IR, FAB-mass, ¹H and ¹³C NMR, EPR and ligand field spectra, which indicated a high-spin state of metal ion with hexa-coordinate environment. ⁵⁷Fe Mössbauer data of the homo-bimetallic complex [Fe₂(imda)₂(H₂O)₃Cl] confirm a high-spin configuration with Fe (±3/2 → 1/2) nuclear transitions and the presence of Kramer's double degeneracy. At RT, the spin–spin interactions of the neighbouring nuclei (Fe³⁺–Fe³⁺ = S_5/2–S_5/2) are anti-ferromagnetically coupled. However, at LNT, the complex acquires a mixed-valent [Fe^III–Fe^II] composition corroborated from the X-band EPR data. CV studies indicated the presence of quasi-reversible redox Cu^II/I, Cu^II/III, Fe^III/II, Fe^III/I and Fe^II/I couples.     

Influence of the RE2O3 (RE = Y,Gd) and CaO nanoadditives on the electromagnetic properties of nanocrystalline Co0.2Ni0.3Zn0.5Fe2O4

The present work reports the influence of the nanoadditives Y₂O₃, Gd₂O₃, and CaO on the magnetic, electrical and dielectric properties of sintered nanoferrites Co_0.2Ni_0.3Zn_0.5Fe₂O₄. All powders were synthesized via the polyol method. XRD analysis showed that except the nanoferrite which was obtained by in an one-post procedure, subsequent calcinations of the as-produced additives were necessary to obtain nanocrystals of the desired phases. The mean particle size inferred from TEM images of the nanoadditives sintered at 1000 °C ranges from 87 nm for Y₂O₃ to 126 nm for CaO. IR spectroscopy provided useful information on the nature of the core and the surface chemistry of the as-produced additives and their associated annealed powders. Upon sintering, it was found that the incorporation of 5 wt.% additives remarkably increased the densification of the doped materials. The most important increase in densification was observed with CaO due to its larger particles. dc M-H hysteresis loops taken at 300 K revealed a superparamagnetic behavior of the produced ferrite/nanoadditives. Additionally, as expected, the ferrite/nanoadditives showed reasonable saturation magnetization and high Curie temperature. The electrical and dielectric properties, namely the resistivity, the loss factor, and the relation frequency were found to be clearly affected by doping. The resistivity decreased with increasing temperature indicating a semiconducting behavior. Further, at room temperature, the highest resistivity was observed with Y₂O₃. The major role was attributed to the high fraction of insulating Y₂O₃ owing to its smallest particles combined with the low Fe²⁺ concentration in the ferrite nanoparticles taking advantages of the moderate sintering temperature. In addition, the dc conductivity was found to follow the Arrhenius law with a slope change observed at the Curie temperature. Further, all the additives clearly affected the ac conductivities of the pure ferrite. The variation of the dielectric permittivity with frequency and temperature was explained on the basis of M-W type of interfacial polarization. Additionally, at high frequencies, the lower dielectric loss was found with Y₂O₃ doping. It was found to be of about 10 times lower than the undoped material and much larger than reported for similar undoped bulk ferrites.