Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Structural and magnetic properties of Co1−xZnxFe2O4 nanorods prepared by the solvothermal annealing method

Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods have been prepared by the thermal decomposition of the corresponding oxalate precursor, which was synthesized by the template-, surfactant-free solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM). The obtained Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods were built by many nanoparticles with average sizes around 20 nm to form one-dimensional arrays. Vibrating sample magnetometry measurements show that the coercivity of the ferrite nanorods decreases with increasing Zn content, whereas the specific saturation magnetization initially increases and then decreases with the increase of Zn content. The maximum saturation magnetization value of the as-prepared sample (Co_0.5Zn_0.5Fe₂O₄) reaches 43.0 emu g⁻¹.     

Microstructure evolution and magnetic properties of Eu doped CuFeO2 multiferroic ceramics studied by positron annihilation

A series of multiferroic ceramics CuFe_1-xEu_xO₂ (x?=?0–0.10) are prepared by traditional solid-state reaction. The effects of Eu doping on the microstructure, vacancy-type defects, and magnetic properties of CuFeO₂ ceramics are investigated systematically by means of X-ray diffraction, Raman spectroscopy, scanning electron microscope, positron annihilation lifetime and physical property measurement system. The results show that no phase transition occurs in the entire range of doping content (x?=?0–0.10), but the single phase structure is damaged by high Eu content (x?=?0.04–0.10). Positron annihilation measurements indicate that the local electron density and the vacancy-type defect concentration increase gradually with the increase in Eu content from 0 to 0.08. Furthermore, abnormal changes in lifetime parameters can be found in x?=?0.10 sample induced by the existence of impurity phase in the system. The magnetic measurements reveal that all the samples exhibit two successive magnetic transitions at T?=?15 and 11?K. In x?=?0.02 sample, the coexistence of ferromagnetism and antiferromagnetism can be found, and a maximum saturation magnetization of 11.548?emu/g at 5?kOe is achieved. The possible reasons for the above observations are discussed in detail.     

Synthesis and magnetic properties of CoAlFe2O4 nanoparticles

Nanosized particles of CoAl_xFe_2-xO₄, where 0?≤?x?≤?2, were synthesized by the sol–gel combustion method and the magnetic properties of these compounds were investigated. According to X-ray diffractograms, the samples are single phase and the crystallite size is between 7 and 25?nm. The room temperature saturation magnetization of the samples was estimated from the cation distribution and ferromagnetic resonance spectra were used to determine the magnetocrystalline anisotropy. The results show that the saturation magnetization and the magnetocrystalline anisotropy vary over a wide range, from maxima of M_s =?0.42?MA/m and K?=?0.39?kJ/m³ for x?=?1.0 to minima of almost zero for x?≈?1.4, a result that could be useful for practical applications of these materials.     

Structural,magnetic and dielectric behavior of Mg1−xCaxNiyFe2−yO4 nano-ferrites synthesized by the micro-emulsion method

Ca–Ni co-substituted samples of nanocrystalline spinel ferrites with chemical formula Mg_1−xCa_xNi_yFe_2−y O₄ (x=0.0–0.6, y=0.0–1.2) were synthesized by the micro-emulsion method and were annealed at 700 °C for 7 h. The synthesized samples were characterized by x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometry (VSM) and dielectric measurements. The XRD and FTIR analysis reveals that single phase samples can be achieved by substituting Ca and Ni ions at Mg and Fe sites respectively in cubic spinel nano-ferrites. The crystallite size of the synthesized samples was found in the range 29–45 nm. The saturation magnetization (M_s) increases from 9.84 to 24.99 emu/g up to x=0.2, y=0.4 and then decreases, while the coercivity (H_c) increases continuously from 94 to 153 Oe with the increase in dopants concentration. The dielectric properties of these nano materials were also studied at room temperature in the frequency range 100 MHz to 3 GHz. The dielectric parameters were found to decrease with the increased Ca–Ni concentration. Further the peaking behavior was observed beyond 1.5 GHz. The frequency dependent dielectric properties of all the samples have been explained qualitatively on the basis of the Maxwell–Wagner two-layer model according to Koop's phenomenological theory. The enhanced magnetic parameters and reduced dielectric properties make the synthesized materials suitable for switching and high frequency applications, respectively.     

Oxygen and chlorine evolution on RuO2 + TiO2 + CeO2 + Nb2O5 mixed oxide electrodes

A systematic investigation was conducted on the mechanism and electrocatalytic properties of O₂ and Cl₂ evolution on mixed oxide electrodes of nominal composition: Ti/[Ru_(0.3)Ti_(0.6)Ce_(0.1−x)]O₂[Nb₂O₅]_(x) (0 ≤ x ≤ 0.1). For the oxygen evolution, a 30 mV Tafel slope is obtained in the presence of CeO₂, while in its absence a 40 mV coefficient is observed. The intrinsic electrocatalytic activity is mainly due to electronic factors, as result of the synergism between Ru and Ce oxides. For chlorine evolution, the Tafel slope (30 mV) is independent on oxide composition. The best global electrocatalytic activity for ClER was observed in the absence of Nb₂O₅ additive. Variation of the voltammetric charge throughout the experiments confirms high CeO₂ content compositions are fragile, due mainly to the porosity caused by CeO₂ presence. On the other hand, Nb₂O₅ addition decreases considerably this instability.     

Structural,morphological, and magnetic properties of ZnxCo1-xFe2O4 (0 ≤ x ≤ 1) prepared using a chemical co-precipitation method

In the present study, the chemical co-precipitation technique was adopted to synthesize Zn_xCo_1-xFe₂O₄ (ZCF) (0?≤ x?≤?1) ferrites. The thermogravimetric-differential thermal analysis results revealed that above 405?°C, the precursor had decomposed and ferrite formation had occurred. The structure and morphology of the prepared ferrite nanoparticles were investigated using X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy (FE-SEM). The synthesized polycrystalline nanoparticles had a cubic spinel structure and the crystallite size was in the range of 6.09–12.98?nm. The prepared ferrites appeared as nearly spherical nanoparticles with a particle size in between 0.13 and 0.23?µm, as confirmed using FE-SEM. The elemental composition was determined using the energy-dispersive X-ray spectroscopy technique. The influence of the Zn-substituted cobalt ferrites (ZCF) on the structural, morphological, and magnetic properties were studied. The magnetic properties of the ZCF samples such as saturation magnetization, remanence magnetization, and coercivity measured at room temperature were 0.387–2.065?emu/g, 0.057–1.282?emu/g, and 60–1834?Oe, respectively. It was confirmed from the nature of the hysteresis loops that the given ZCF samples can be considered as a soft magnetic material.     

Studies on syntheses and properties of novel CeO2/polyimide nanocomposite films from Ce(Phen)3 complex

A series of cerium dioxide (CeO₂)/polyimide (PI) nanocomposites were successfully prepared from Ce(Phen)₃ and polyamic acid (PAA) via the solution direct-dispersing method, followed by a step thermal imidization process. TGA and XPS studies showed that the cerium complex decomposed to form CeO₂ during the thermal imidization process at 300 °C. SEM observation showed that the formed CeO₂ as nanoparticles was well dispersed in polyimide matrix with a size of about 50-100 nm for samples with different contents of CeO₂. Thermal analysis indicated that the introduction of CeO₂ decreased the thermal stability of nanocomposite films due to the decomposition of Ce(Phen)₃ in the imidization process, while the glass transition temperature (T_g) increased obviously, especially nanocomposite films with high loading of CeO₂ exhibited a trend of disappearance of T_g. DMTA and static tensile measurements showed that the storage modulus of nanocomposite films increased, while the elongation at break decreased with increasing CeO₂ content.     

Co-doped ceria-based solid solution in the CeO2-M2O3-CaO, M = Sm, Gd system

The Pechinni method (A) as well as hydrothermal treatment (B) of co-precipitated CeO₂-based gels with NaOH solution were used to synthesise pure CeO₂, and CeO₂-based solid solutions with formula Ce_1−xM_xO₂, Ce_1−x(M_0.5Ca_0.5)_xO₂ M = Gd, Sm for 0.15 < x < 0.3 nanopowders. The thermal evolution of CeO₂-based precursors during heating them up to 1000 °C was monitored by thermal (TG, DTA) analysis and X-ray diffraction method. All nanopowders and samples sintered were found to be pure CeO₂ or ceria-based solutions with fluorite-type structure. The microstructure of CeO₂-based sintered samples at 1500 °C (A) or 1250 °C (B) was observed for 2 h under the scanning electron microscope. The electrical properties of singly Ce_1−xM_xO₂ or doubly doped CeO₂-based samples with formula Ce_1−x(M_0.5Ca_0.5)_xO₂, M = Gd, Sm, 0.15 < x < 0.30 were investigated by means of the ac impedance spectroscopy method throughout the temperature range of 600-800 °C. It has been stated that partial substitution of calcium by samarium or calcium by gadolinium in the Ce_1−x(M_0.5Ca_0.5)_xO₂, M = Gd, Sm solid solutions leads to ionic conductivity enhancement comparable with only samaria- or gadolina-doped ceria. The CeO₂-based samples with small-grained microstructures obtained from powders synthesised by hydrothermal method exhibited better ionic conductivity than samples with the same composition obtained from powders synthesised by the Pechinii method. The stability of the electrolytic properties of selected co-doped ceria sinters in fuel gases (H₂, CH₄) as well as exhaust gases from diesel engine was also investigated. The co-doped Ce_0.8(Sm_0.5Ca_0.5)_0.2O₂ or Ce_0.85(Gd_0.5Ca_0.5)_0.15O₂ dense samples would appear be to more adequate oxide electrolytes than Ce_1−xM_xO₂, M = Sm, Gd and x = 0.15 or 0.2 for electrochemical devices operating at temperatures ranging from 600 to 700 °C.     

sol-gel法制备CeO2-TiO2/凹凸棒石复合材料的催化性能

以凹凸棒石(ATP)为载体,Ce(NO₃)₃·6H₂O和Ti(OBu)₄为原料,冰醋酸为抑制剂,采用溶胶-凝胶法制备CeO₂-TiO₂/ATP纳米复合材料。利用TG-DSC、TEM、XRD和N₂吸附/脱附仪对复合材料进行表征,考察铈钛摩尔比对所制备样品催化降解罗丹明B溶液性能的影响。结果表明,当Ce/Ti≥5/5时,具有立方萤石结构的氧化物颗粒以固溶体形式均匀分布在ATP表面,颗粒尺寸约5~10 nm;随Ti⁴⁺的进一步增加,样品中的CeO₂结晶不完全;当Ce/Ti<3/7时,样品中出现锐钛矿型TiO₂的分离相。适量的Ti⁴⁺掺杂能促进CeO₂产生较多的结构缺陷,有利于增加晶格氧空位的浓度,提高样品的催化活性。对罗丹明B的催化降解实验表明,当Ce/Ti=5/5时,样品的催化性能较好,对罗丹明B溶液的化学需氧量(COD)去除率可达96%以上。     

Synthesis and optical properties of Cr-doped Ba2In2O5 orange-brown oxides

Cr-doped Ba₂In_2-xCr_xO_5+y (0?≤?x?≤?0.5) orange-brown inorganic oxides have been successfully synthesized by solid-state reaction. X-ray diffraction (XRD) patterns show that their crystal structures transform from orthorhombic to cubic by increasing the Cr doping amount. Field emission scanning electron microscopy (FESEM) measurements show powder particles of irregular shape with average particle size of about 10?µm. The colors of the compounds are tuned from light yellow (x?=?0) to orange (x?=?0.1) and then to dark brown (x?=?0.5). X-ray photoelectron spectroscopy and UV–Vis absorption spectroscopy demonstrate the oxidation state of Cr to be +?6 and the change in color to be due to the metal-ligand charge transfer of Cr⁶⁺-O^2-.     

Synthesis and magnetic properties of monodisperse CoFe2O4 nanoparticles coated by SiO2

The monodisperse CoFe₂O₄ nanoparticles were synthesized by a modified chemical coprecipitation method. Coating SiO₂ on the surface of the CoFe₂O₄ nanoparticles was carried out to keep single domain particles non-interacting with cubic magnetocrystalline anisotropy. The Curie temperatures (T_c) of the monodisperse CoFe₂O₄ nanoparticles can be accurately measured because the SiO₂ shells prevented the aggregation and growth of nanoparticles at high temperature. The magnetic properties of the CoFe₂O₄@SiO₂ nanoparticles with core-shell structure in a wide temperature range (300～950?K) were investigated. It is remarkable that the coercive field (H_c) of CoFe₂O₄ nanoparticles increased from about 760?Oe to 1806?Oe after being coated with SiO₂, which increased by 137.6% compared to the uncoated samples at 300?K. The saturation magnetization (M_s) of the CoFe₂O₄@SiO₂ nanoparticles is 34.59?emu/g, which is about 52% of the naked CoFe₂O₄ nanoparticles value (66.51?emu/g) at 300?K. The hysteresis loops of the CoFe₂O₄@SiO₂ nanoparticles showed an orderly magnetic behavior at high temperature, such as the M_s, remanence magnetization (M_r) and H_c decreased as temperature increasing, being equal to zero near T_c. This is a good indication that the CoFe₂O₄@SiO₂ nanoparticles are suitable for a wide variety of technological applications at high temperature.     

Nb modified structural,magnetic and magnetocaloric properties of double perovskite Ba2FeMo1−xNbxO6

A systematic study focusing on the effect of Niobium (Nb) doping on the structural, magnetic and magnetocaloric properties of Ba₂FeMoO₆ samples is presented here. The samples of interest Ba₂FeMo_1?xNb_xO₆ (0 ≤ x ≤ 0.4) were prepared using the solid state reaction method and were confirmed to possess a cubic structure with Fm-3m space group using the X-ray diffraction analysis and Rietveld refinement. A second order of ferromagnetic phase transition was recorded in both the pure as well as the Nb doped samples using the temperature dependent magnetization and Arrott plots analysis. The pristine Ba₂FeMoO₆ (BFMO) sample indicated a spontaneous magnetization (34.6 emu/g at 100 K) with a relatively sharp magnetic transition at the Curie temperature (T_C) of 315 K as compared to the doped samples. A magnetic entropy change of 0.93 Jkg^?1K^?1 at an applied magnetic field of 2.5 T was measured for the pure BFMO sample. The doped BFMO samples with Mo partially substituted by Nb however, were observed to effectively modify the T_C accompanied by a decrease in magnetization. The results investigated in this work suggest that the magnetic and magnetocaloric properties of the BFMO can be tailored by controlled Nb doping which is of significant importance in order to realize the numerous potential applications of the material in the magnetic refrigeration technology.     

Au/Ce1−xZrxO2 as effective catalysts for low-temperature CO oxidation

The physico-chemical properties and activity of Ce-Zr mixed oxides, CeO₂ and ZrO₂ in CO oxidation have been studied considering both their usefulness as supports for Au nanoparticles and their contribution to the reaction. A series of Ce_1−xZr_xO₂ (x = 0, 0.25, 0.5, 0.75, 1) oxides has been prepared by sol–gel like method and tested in CO oxidation. Highly uniform, nanosized, Ce-Zr solid solutions were obtained. The activity of mixed oxides in CO oxidation was found to be dependent on Ce/Zr molar ratio and related to their reducibility and/or oxygen mobility. CeO₂ and Ce_0.75Zr_0.25O₂, characterized by the cubic crystalline phase show the highest activity in CO oxidation. It suggests that the presence of a cubic crystalline phase in Ce-Zr solid solution improves its catalytic activity in CO oxidation. The relation between the physico-chemical properties of the supports and the catalytic performance of Au/Ce_1−xZr_xO₂ catalysts in CO oxidation reaction has been investigated. Gold was deposited by the direct anionic exchange (DAE) method. The role of the support in the creation of catalytic performance of supported Au nanoparticles in CO oxidation was significant. A direct correlation between activity and catalysts reducibility was observed. Ceria, which is susceptible to the reduction at the lowest temperature, in the presence of highly dispersed Au nanoparticles, appears to be responsible for the activity of the studied catalysts. CeO₂-ZrO₂ mixed oxides are promising supports for Au nanoparticles in CO oxidation whose activity is found to be dependent on Ce/Zr molar ratio.     

Electronic structure and magnetic properties of Ba1-xSrxCoFe11O19 hexaferrites

We have prepared Ba_1-xSr_xCoFe₁₁O₁₉ hexaferrite nanoparticles (NPs) by using a co-precipitation method. The crystal/electronic structures and magnetic properties were then studied. Results revealed that all Ba_1-xSr_xCoFe₁₁O₁₉ NPs with particle sizes of 100–300?nm crystallized in a hexagonal structure. Both the particle shape and the unit-cell parameters are changed when Sr content (x) increases. The analysis of the electronic structure based on the Fe and Co K-edge XAS spectra proved the oxidation states of Fe and Co to be 3?+?and 2?+?, respectively, which are stable versus an x change in Ba_1-xSr_xCoFe₁₁O₁₉. Local-structural studies also revealed the average bond length between Fe and O of 1.89–1.91?Å less changed by Sr doping. Though the electronic structures of Fe and Co were unchanged, the studies about the magnetic property demonstrated a strong dependence of M_s and H_c on Sr doping. While M_s decreases from 46.1?emu/g for x?=?0–34.2?emu/g for x?=?1, H_c tends to increase from 1630?Oe for x?=?0 to ~ 2200?Oe for x?=?0.5, but slightly decreases to 2040?Oe for x?=?1. We think that the addition of the exchange interaction between Fe³⁺ and Co²⁺ ions and the changes of local-geometric structures and microstructures influenced directly M_s and H_c of NPs.     

Microstructure and dielectric properties of Ba0.6Sr0.4TiO3-MgAl2O4 composite ceramics

(1 − x)Ba_0.6Sr_0.4TiO₃-xMgAl₂O₄(x = 25, 30, 35 and 40 wt%) composite ceramics were prepared by conventional solid-state reaction method. The microstructures, dielectric properties and tunability of the composites have been investigated. The XRD patterns analysis reveals two crystalline phases, a cubic perovskite structure Ba_0.6Sr_0.4TiO₃ (BST) and a spinel structure MgAl₂O₄ (MA). SEM observations show that the BST grains slightly dwindle and agglomerate with increasing amounts of MA. A dielectric peak with very strong frequency dispersion is observed at higher MA content, and the Curie temperature shifts to a higher temperature with increasing MA content. The ceramic sample with 30 wt% MA has the optimized properties: the dielectric constant is 1503, the dielectric loss is 0.003 at 10 kHz and 25 °C, the tunability is 23.63% under a dc electric field of 1.0 kV/mm, which is suitable for ferroelectric phase shifter.     

Improvement of electrochemical stability of LiMn2O4 by CeO2 coating for lithium-ion batteries

CeO₂-coated LiMn₂O₄ spinel cathode was synthesized using two-step synthesis method. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. The results of the electrochemical performances on CeO₂-coated electrode are compared to those of electrodes based on LiMn₂O₄ spinel without CeO₂ coating. CeO₂-coated LiMn₂O₄ cathode improved the cycling stability of the electrode. The capacity retention of 2 wt% CeO₂-coated LiMn₂O₄ was more than 82% after 150 cycles between 3.0 and 4.4 V at room temperature and 82% after 40 cycles at elevated temperature of 60 °C. The amounts of dissolved manganese-ions in CeO₂-coated LiMn₂O₄ significantly are smaller than pristine LiMn₂O₄ systems especially at elevated temperatures. Surface-modified LiMn₂O₄ can suppress the dissolution reaction of manganese-ions at elevated temperature and clearly improve the cyclability of the spinel LiMn₂O₄ cathode materials.     

Solid-state electrochromic devices with Nb2O5:Mo thin film and gelatin-based electrolyte

A gelatin-based electrolyte has been developed and characterized by impedance spectroscopy, X-ray diffraction, UV-vis-NIR spectroscopy and atomic force microscopy (AFM). The heat treatment temperature was found the key factor affecting its ionic conductivity that increases from 1.5 × 10⁻⁵ S/cm to 4.9 × 10⁻⁴ S/cm by heating from room temperature up to 80 °C. The temperature dependence of the ionic conductivity exhibits an Arrhenius behavior. EC-devices with the configuration K-glass/Nb₂O₅:Mo EC-layer/gelatin-based electrolyte/(CeO₂)_x(TiO₂)_1−x ion-storage (IS) layer/K-glass, have been assembled and characterized. They show a good long time cyclic stability, but the change of the optical density measured at 550 nm after 25 000 cycles was only 0.13.     

Optical and ferromagnetic properties of hydrothermally synthesized CeO2/CuO nanocomposites

Nanostructured CeO₂/CuO composites are synthesized using a facile hydrothermal reaction. Results signify that Cu ions prefer to enter into CeO₂ lattice forming solid solution at low concentration, and would be transformed into CuO phase at moderate concentration. Moreover, the addition of CuO species into CeO₂ promotes the reduction of Ce⁴⁺ and the creation of oxygen vacancy (V_O) defects. Raman analyses confirm V_O concentration initially increases and then decreases with the increasing CuO phase and the sample Ce1Cu2 exhibits the highest defect concentration. The room temperature ferromagnetic behavior is observed firstly in CeO₂/CuO nonmagnetic system and the maximal saturation magnetization appears in Ce1Cu2. The emergent ferromagnetism appears to be relevant to the extensive V_O defects, which can be interpreted by the indirect double-exchange model. The synthetic interaction between CeO₂ and CuO results in the redshift of the bandgap in prepared CeO₂/CuO nanocomposites.     

Structural and magnetic properties of NiFe2−xBixO4 (x = 0, 0.1, 0.15) nanoparticles prepared via sol-gel method

NiFe_2−xBi_xO₄ (x = 0, 0.1, 0.15) nanopowders were synthesized via sol-gel method. The precursor gels were calcined at 773 K in air for 1 h to obtain the pure nanostructured NiFe_2−xBi_xO₄ spinel phase. The crystal structure and magnetic properties of the substituted spinel series of NiFe_2−xBi_xO₄ have been investigated by means of ⁵⁷Fe Mössbauer spectroscopy, transmission electron microscopy and alternating gradient force magnetometry. Mössbauer spectroscopic measurements revealed that Bi³⁺ cations tend to occupy octahedral positions in the structure of the substituted ferrite, i.e., the crystal-chemical formula of the as-prepared nanoparticles may be written as: (Fe)[NiFe_1−xBi_x]O₄ (x = 0, 0.1, 0.15), where parentheses and square brackets enclose cations on sites of tetrahedral and octahedral coordination, respectively. Selective area electron diffraction studies provided evidence that the samples of the NiFe_2−xBi_xO₄ series, independently of x, exhibit the cubic spinel structure. The values of the saturation magnetization and the coercive field of NiFe_2−xBi_xO₄ nanoparticles were found to decrease with increasing degree of bismuth substitution.