Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides

Novel cobalt oxide doped ZnFe₂O₄-Fe₂O₃-ZnO mixed oxides with the Zn/Fe molar ratio of 1/2 were synthesized with a citric acid complex method. The effects of cobalt oxide and calcination temperature on phase composition and photocatalytic activity of the mixed oxides were investigated. X-ray diffraction (XRD) analysis revealed that there were mainly ZnFe₂O₄, α-Fe₂O₃, amorphous ZnO and Fe₂O₃ in the 6 mol% cobalt oxide doped products calcined at 500 °C. 5-10 mol% cobalt oxide doping could significantly enhance the formation of ZnFe₂O₄ and altered the phase composition of the mixed oxides. Experimental results showed that cobalt oxide doping could remarkably improve the photocatalytic activity of the mixed oxides for phenol degradation. The 6 mol% cobalt oxide doped mixed oxides calcined at 500 °C exhibited better photocatalytic activity as compared with other samples.     

Structure and magnetic property of CoFe2−xSmxO4 (x = 0–0.2) nanofibers prepared by sol–gel route

CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers with diameters about 100–300 nm have been prepared using the organic gel-thermal decomposition method. The composition, structure and magnetic properties of the CoFe_2−xSm_xO₄ nanofibers were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, inductive coupling plasma mass analyzer and vibrating sample magnetometer. The CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers obtained at 500–700 °C are of a single spinel structure. But, at 800 °C with a relatively high Sm content of 0.15–0.2 the spinel CoFe_2−xSm_xO₄ ferrite is unstable and the second phase of perovskite SmFeO₃ occurs. The crystalline grain sizes of the CoFe_2−xSm_xO₄ nanofibers decrease with Sm contents, while increase with the calcination temperature. This grain reduction effect of the Sm³⁺ ions doping is largely owing to the lattice strain and stress induced by the substitution of Fe³⁺ ions with larger Sm³⁺ ions in the ferrite. The saturation magnetization and coercivity increase with the crystallite size in the range of 8.8–57.3 nm, while decrease with the Sm content from 0 to 0.2 owing to a smaller magnetic moment of Sm³⁺ ions. The perovskite SmFeO₃ in the composite nanofibers may contribute to a high coercivity due to the interface pinning, lattice distortion and stress in the ferrite grain boundary fixing and hindering the domain wall motion.     

Spinel ferrite MFe2O4 (M = Ni,Co, or Cu) nanoparticles prepared by a proteic sol-gel route for oxygen evolution reaction

In this work, spinels of MFe₂O₄ (M = {Ni, Co, Cu}) were successfully prepared by proteic sol-gel method using commercial flavorless gelatin as a chelating agent. To break down aggregated particles, the samples were milled in alcohol at 400 rpm for 1 h. According to Rietveld refinements and transmission electron microscopy, the samples had crystallite and particle sizes in the range of 36–53 nm and 44–147 nm, respectively, confirming the as-prepared samples in a nanoscale. X-ray diffraction and Rietveld refinement confirmed that the samples are single phase. In addition, Mössbauer spectroscopy analysis and X-ray photoelectron spectroscopy revealed the mixed spinel composition. Besides, X-ray photoelectron spectroscopy showed surface oxygen vacancies, given by ratio areas between oxygen vacancies (O_V) and oxygen in the lattice (O_L), of 0.63, 0.27 and 0.10 for NiFe₂O₄, CuFe₂O₄ and CoFe₂O₄ powders, respectively. Magnetic measurements showed ferrimagnetic behavior for all samples. Toward oxygen evolution reaction (OER), copper-oxygenated groups on the CuFe₂O₄ nanoparticle surface may play an important role, once CuFe₂O₄ showed superior electrocatalytic performance, with overpotentials of 369 mV (CuFe₂O₄) < 386 mV (NiFe₂O₄) < 448 mV (CoFe₂O₄) at a current density of 10 mA cm^?2 and Tafel slopes of 76.3 mV dec^-1 (CuFe₂O₄), 85.7 mV dec^-1 (NiFe₂O₄) and 148.1 mV dec^-1 (CoFe₂O₄). All samples exhibited mechanical stability during the OER process.     

Crystallite structure,microstructure, dielectric,and piezoelectric properties of (Pb1.06−xBax)(Nb0.94Ti0.06)2O6 piezoelectric ceramics prepared using calcined powders with different phases

In an attempt to obtain dense lead metaniobate-based ceramics with improved dielectric and piezoelectric properties, the (Pb_1.06−xBa_x)(Nb_0.94Ti_0.06)₂O₆ (x = 0, 0.04, 0.08, 0.12) piezoelectric ceramics were prepared separately from the two kinds of calcined powders, i.e., the powders with the rhombohedral phase and orthorhombic phase. For obtaining the calcined powders with the different phases, two different calcination temperatures of 900 °C and 1250 °C were chosen. The calcined powders were characterized using X-ray diffraction, scanning electron microscope, laser particle size analyzer and differential scanning calorimetry. Effects of the phase structures of the calcined powders on crystallite structure, microstructure, dielectric and piezoelectric properties of the ceramics were studied in detail. The lattice parameters and grain size of the ceramics are related to the phase structures of the calcined powders. The doping of Ba²⁺ has an influence on the dielectric and piezoelectric properties of the ceramics. The ceramics with x = 0.08 fabricated from the calcined powders with the orthorhombic phase demonstrate the optimum dielectric and piezoelectric properties.     

Magnetic properties and methylene blue adsorptive performance of CoFe2O4/activated carbon nanocomposites

Owing to the unique microporous structure and high specific surface area, activated carbon (AC) could act as a good carrier for functional materials. In this paper, CoFe₂O₄/AC nanocomposites were prepared by a facile hydrothermal method for the adsorption of dyes in wastewater. The results indicated that CoFe₂O₄ nanoparticles presented the spinel structure and existed in the pores of AC. The saturation magnetization (Ms) increased with the CoFe₂O₄ content, while the surface area and pore volume decreased. For the larger magnetic moment, very few CoFe₂O₄ were needed to maintain the higher surface area of CoFe₂O₄/AC nanocomposites. The sample-5 (CoFe₂O₄:C = 1:200) possessed the surface area of 1096.85 m² g⁻¹ (close to 1243.35 m² g⁻¹ of AC) and Ms of 5.11 emu g⁻¹, which were sufficient for magnetic separation in wastewater treatment. 99% methylene blue could be adsorbed in 50 min, and then the CoFe₂O₄/AC nanocomposites could be separated from the solution easily by an outer magnet.     

Substitutional effect on structural and dielectric properties of Ni1−xAxFe2O4 (A = Mg,Zn) mixed spinel ferrites

The Ni_1−xA_xFe₂O₄ (A = Zn, Mg; x = 0.0, 0.5) ferrites synthesized by chemical co-precipitation method. X-ray diffraction and Raman spectroscopy reveals that all the ferrite samples are in single-phase cubic spinel structure with Fd3m space group. The lattice parameter enhances with Mg and Zn substitution. Raman spectroscopy identifies a doublet like nature of A_1g mode for all the three ferrites. A blue shift in Mg doped ferrite and a red shift in Zn doped ferrite has been observed as compared to parent NiFe₂O₄. Frequency dependent dielectric response confirms the dielectric polarization and electrical conduction mechanism. The minimum value of loss tangent (∼0.03) at 5 KHz suggests that Ni_1−xA_xFe₂O₄ is effective material for microwave application. The activation energy for NiFe₂O₄, Ni_0.5Mg_0.5Fe₂O₄ and Ni_0.5Zn_0.5Fe₂O₄ are found to be 0.28 eV, 0.29 eV and 0.31 eV, respectively.     

The effect of Tb doping on the structure and spectroscopic properties of MgAl2O4 nanopowders

In this paper, a modified sol-gel method was employed to prepare nanostructured MgAl₂O₄ spinel powders doped with Tb³⁺ ions and thermally treated at 700 and 1000 °C for 3 h. The structural properties of the prepared at 700 and 1000 °C powders where characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to obtained XRD patterns the formation of single-phase spinels after calcination was confirmed. The XRD analyses demonstrated that the powders were single-phase spinel nanopowders with high crystallite dispersion. The Rietveld method was applied to calculate lattice parameters. The averaged spinel particle size was determined to be ∼10 nm for calcination at 700 °C and ∼20 nm at 1000 °C. The emission and excitation spectra measured at room and low temperature (77 K) for the samples calcined at 700 and 1000 °C demonstrated characteristic spectra of Tb³⁺ ions. The effect of MgAl₂O₄:Tb³⁺ grain sizes on luminescence properties was noticed.     

Preparation,phase structure and microwave dielectric properties of a new low cost MgLi2/3Ti4/3O4 compound

A novel Li-based spinel compound with the composition of MgLi_2/3Ti_4/3O₄ was synthesized by the conventional solid-state reaction method. The phase structure was studied by X-ray diffraction (XRD) technique. When the calcination temperature was over 1050 °C, a single phase compound which has a cubic structure [Fd-3m (227)] with cell parameters of a = 8.4057 Å, V = 593.91 Å³, ρ = 3.51 g cm⁻³ and Z = 8 was obtained. MgLi_2/3Ti_4/3O₄ ceramic could be well densified after sintering above 1125 °C. The microwave dielectric properties were measured using a microwave vector network analyzer in the frequency range of 7–9 GHz MgLi_2/3Ti_4/3O₄ ceramic sintered at 1125 °C for 2 h showed microwave dielectric properties of ?_r = 20.2, Q × f = 62,300 GHz, and τ_f = −27.1 ppm °C⁻¹. Furthermore, 0.95MgLi_2/3Ti_4/3O₄–0.05CaTiO₃ ceramic sintered at 1200 °C for 2 h exhibited good properties of ?_r = 22.6, Q × f = 48,000 GHz, and τ_f = −2.3 ppm °C⁻¹.     

Synthesis of the nanocrystalline CoFe2O4 ferrite thin films by a novel sol-gel method using glucose as an additional agent

Polycrystalline and nanometer-sized CoFe₂O₄ ferrite thin films are successfully synthesized using glucose as an addition agent. The thermal gravimetric/differential thermal analyzer, X-ray diffractometer, electron diffraction, scanning electron microscope, atomic force microscope and vibrating sample magnetometer are used to characterize the effects of the calcination temperature on the crystalline structure, morphology and magnetic properties of the Co-ferrite thin films. CoFe₂O₄ ferrite thin films have a single phase inverse spinel structure and are crystallized at and above 300 °C which is much lower than the required temperature in the traditional ceramic method (about 500-600 °C). Co-ferrite thin films annealed at relative low temperature of 400 °C show very small particle size with average of 32 nm and excellent magnetic properties for information storage applications.     

Paederia foetida Linn. promoted synthesis of CoFe2 O4 and NiFe2 O4 nanostructures and their photocatalytic efficiency

A facile method of synthesis of cobalt ferrite (CoFe₂ O₄) and nickel ferrite (NiFe₂ O₄) nanoparticles (NPs) was developed using urea as a hydroxylating agent and Paederia foetida Linn. (family: Rubiaceae) leaf extract as a bio‐template. The synthesised ferrite NPs were characterised in a detailed manner by powder X‐ray diffraction (XRD), transmission electron microscopy, Fourier transform‐infrared spectroscopy and vibrating sample magnetometer analysis. The XRD patterns revealed the formation of cubic face‐centred phase for both CoFe₂ O₄ and NiFe₂ O₄ NPs. These quasi‐spherical particles of CoFe₂ O₄ and NiFe₂ O₄ were shown to have sizes in the range of 10–80 and 5–50 nm, respectively. The photocatalytic activity of metal ferrites was evaluated in H₂ O₂ assisted oxidative degradation of methylene blue (MB) and rhodamine B (RhB) under irradiation of solar light. Both metal ferrite photocatalysts exhibited pronounced activity in degradation of MB and RhB, respectively, but relatively higher activity was observed for NiFe₂ O₄. After completion, the catalysts were recovered using an external magnet. Recycling of these recovered catalysts up to five times showed no noticeable change in the efficiency.Inspec keywords: nanoparticles, nanofabrication, photochemistry, catalysts, cobalt compounds, nickel compounds, ferrites, X‐ray diffraction, transmission electron microscopy, Fourier transform infrared spectra, crystal structure, dyesOther keywords: Paederia foetida Linn, nanostructures, photocatalytic efficiency, cobalt ferrite nanoparticles, nickel ferrite nanoparticles, hydroxylating agent, leaf extract, bio‐template, powder X‐ray diffraction, transmission electron microscopy, Fourier transform‐infrared spectroscopy, vibrating sample magnetometer analysis, cubic face‐centred phase, quasi‐spherical particles, photocatalytic activity, methylene blue, rhodamine B, size 5 nm to 80 nm, CoFe₂ O₄ , NiFe₂ O₄      

Synthesis and characterizations of Nd doped SrFe12O19 nanoparticles

This is the first report ever on Nd³⁺ doped M-type hexaferrite nanoparticles: SrNd_xFe_12−xO₁₉ (0 ≤ x ≤ 1) prepared by citrate precursor using the sol–gel technique followed by gel to crystallization. The influence of the Nd³⁺ substitution, Fe³⁺/Sr²⁺ molar ratio and the calcination temperature on the crystallization of ferrite phase have been examined using powder X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), inductance capacitance resistance meter bridge (LCR) and vibrating sample magnetometer (VSM). The structural analysis reveals that the Nd³⁺ ions rearrange themselves in the host lattice without disturbing the parent lattice and Fe³⁺/Sr²⁺ molar ratio less than 12 is more favorable to achieve single phase hexaferrite at calcination temperature 900 °C for 4 h. Mid-IR analysis confirms that Nd³⁺ occupies the octahedral site. Detailed studies of electrical properties of prepared materials have been investigated in the frequency range 100–1000 Hz at room temperature by LCR meter and two probe technique. The result shows that the electrical properties strongly depend upon the frequency of applied field and dopant concentration. The magnetic measurements showing a considerable improvement in coercivity with the substitution of Nd³⁺ on iron sites, while the unsubstituted hexaferrites have highest value of specific saturation magnetization.     

The effect of Cu content on the structure of Ni1−xCuxFe2O4 spinels

A series of Ni_1−xCu_xFe₂O₄ (0 ≤ x ≤ 0.5) spinels were synthesized employing sol-gel combustion method at 400 °C. The decomposition process was monitored by thermal analysis, and the synthesized nanocrystallites were characterized by X-ray diffraction, transmission electron microscopy, infra-red and X-ray photoelectron spectroscopy. The decomposition process and ferritization occur simultaneously over the temperature range from 280 °C to 350 °C. TEM indicates the increase of lattice parameter and particle size with the increase of copper content in accordance with the XRD analysis. Cu²⁺ can enter the cubic spinel phase and occupy preferentially the B-sites within x = 0.3, and redundant copper forms CuO phase separately. A broadening of the O 1s region increases with the increment of copper content compared to pure NiFe₂O₄, showing different surface oxygen species from the spinel and CuO. Cu²⁺ substitution favors the occupancy of A-sites by Fe³⁺.     

Structural and magnetic properties of CoFe2O4 thin films deposited by laser ablation on Si (001) substrates

Cobalt ferrite (CoFe₂O₄) thin films have been deposited on Si (001) substrates, with different substrate temperatures (T_dep = 25 °C − 600 °C). The films were prepared by pulsed laser ablation with a KrF excimer laser (wavelength λ = 248 nm). The oxygen pressure during deposition was 2 × 10⁻² mbar. The films structure was studied by X-ray diffraction (XRD) and their surface was examined by scanning electron microscopy (SEM). The magnetic properties were measured with a vibrating sample magnetometer (VSM). For low deposition temperatures, the films presented a mixture of a CoFe₂O₄ phase, with the cubic spinel structure, and cobalt and iron antiferromagnet oxides with CoO and FeO stoichiometries. As the deposition temperature increased, the CoO and FeO relative content strongly decreased, so that for T_dep = 600 °C the films were composed mainly by polycrystalline CoFe₂O₄. The magnetic hysteresis cycles measured in the films were horizontally shifted due to an exchange coupling field (H_exch) originated by the presence of the antiferromagnetic phases. The exchange field decreased with increasing deposition temperature, and was accompanied by a corresponding increase of the coercivity and remanence ratio of the cycles. This behavior was due to the strong reduction of the CoO and FeO content, and to the corresponding dominance of the CoFe₂O₄ phase on the magnetic properties of the thin films.     

Etude des solutions solides entre le sesquioxyde de fer cubique γ-Fe2O3 et le ferrite de zinc ZnFe2O4

The authors have prepared metastable solid solutions between cubic iron sesquioxide γ-Fe₂O₃ and zinc ferrite ZnFe₂O₄. They give the main characteristics of these defect spinels. Fe³⁺ ions and vacancies are replaced by Zn²⁺ ions on tetrahedral sites. The lattice parameter and the thermal stability increase with the substitution rate. The magnetic behavior is comparable to that observed for solid solutions M_1?yZn_yFe₂O₄.     

Effect of annealing on the microstructure of NiFe1.925Dy0.075O4 thin films

Dysprosium-doped nickel-ferrite (NiFe_1.925Dy_0.075O₄) thin films were fabricated using RF sputter-deposition. Structural studies indicate that the effect of post-deposition annealing is significant on structural evolution in NiFe_1.925Dy_0.075O₄ films. As-grown NiFe_1.925Dy_0.075O₄ films were amorphous. Annealing (T_a) in air at 450-1000 °C results in the formation of nanocrystalline NiFe_1.925Dy_0.075O₄ films, which crystallize in the inverse spinel structure. The average grain size (L) increases from 5 to 40 nm with increasing T_a from 450 to 1000 °C. Lattice constant of NiFe_1.925Dy_0.075O₄ films is higher compared to that of NiFe₂O₄ due to partial substitution of Dy³⁺ ions for Fe³⁺ ions. The lattice parameter increases from 8.353 to 8.362 Å with increasing T_a from 450 to 1000 °C which is attributed to the lattice-strain developed in the NiFe_1.925Dy_0.075O₄ films with increasing T_a. The corresponding density of NiFe_1.925Dy_0.075O₄ films increases from 3.2 to 3.9 g/cm³ with increasing annealing temperature. Magnetization measurements indicate the ferromagnetic behavior of all the films while the coercive field values at 300 K are found to be 0.0134 T and 0.0162 T for as grown and T_a = 1000 °C films, respectively.     

An electron microscope study of thin ferrite films prepared by the oxidation of high purity vacuum-evaporated metal thin films

The oxidation of thin films of nickel, cobalt, iron, NiFe₂ and CoFe₂ has been investigated between 200 and 1200° C. The oxidation products for the elemental metals differ from the oxidation products observed in previous work upon bulk material. The oxidation mechanism proposed for bulk material is in general still valid in the thin film situation. Above oxidation temperatures of approximately 850° C both NiFe₂ and CoFe₂ form the respective ferrites, although in the case of nickel ferrite, traces of the -Fe₂O₃ tetragonal superstructure can still be detected at oxidation temperatures of 1200° C. Films of nickel ferrite and cobalt ferrite upon single-crystal magnesium oxide substrates, produced by oxidation of vacuum-deposited NiFe₂ and CoFe₂ thin films, have been investigated by transmission and scanning electron microscopy. It has been found that (100) nickel ferrite prepared by this technique grows epitaxially upon (100) magnesium oxide.     

Synthesis of nanocrystalline xCuFe2O4-(1 − x)BiFeO3 magnetoelectric composite by chemical method

xCuFe₂O₄-(1 − x)BiFeO₃ spinel-perovskite nanocomposites with x = 0.1, 0.2, 0.3 and 0.4 were prepared using citrate precursor method. X-ray diffraction (XRD) analysis showed phase formation of xCuFe₂O₄-(1 − x)BiFeO₃ calcined at 500 °C. Transmission electron microscopy (TEM) shows formation of nanocrystallites of xCuFe₂O₄-(1 − x)BiFeO₃ with an average particle size of 40 nm. Variation of dielectric constant and dielectric loss with frequency showed dispersion in the low frequency range. Coercivity, saturation magnetization and squareness have been found to vary with concentration of ferrite phase and annealing temperature due to the increase in crystallite size. Squareness and coercivity increased with an increase in annealing temperature up to 500 °C and then decreased with a further increase in temperature to 600 °C. Magnetoelectric effect of the nanocomposites was found to be strongly depending on the magnetic bias and magnetic field frequency.     

Formation of NiFe2O4 nanoparticles by mechanochemical reaction

Preparation of nanosized NiFe₂O₄ particles by mechanochemical reaction(NiO+α-Fe₂O₃) and subsequent thermal treatment was investigated using X-ray diffraction (XRD). Thermal treatment of the as-milled powder at 700 °C for 1 h led to the formation of NiFe₂O₄ nanoparticles with an average crystal size of about 23 nm. Effect of thermal treatment temperature on the crystal size of the nanoparticles was studied. The mechanism of nanoparticles growth was primarily discussed. The activation energy of NiFe₂O₄ nanoparticle formation during calcination was calculated to be 16.6 kJ/mol.