分级多孔Cafe2O4/C的合成及其微波催化活性

以天然木棉为模板,利用造孔及纳米颗粒自组装两步法合成了分级多孔的Cafe₂O₄/C复合催化剂. Cafe₂O₄/C复合催化剂保留了木棉模板的中空纤维形貌,且该中空纤维是由碳及均匀分布在碳表面的Cafe₂O₄纳米颗粒组成. 该复合催化剂具有较强的甲基紫微波催化降解活性. 研究了Cafe₂O₄负载量、微波功率、催化剂用量、甲基紫的初始浓度和pH值对微波诱导甲基紫降解的影响. 结果表明,Cafe₂O₄/C微波降解甲基紫的催化反应具有较高的反应速率和较短的反应时间. 其降解反应符合一级动力学模型. Cafe₂O₄/C 高的催化活性得益于催化反应和吸附特性之间的协同作用.     

Low-temperature sintering effects on NASICON-structured LiSn<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript> solid electrolytes prepared via citric acid-assisted sol-gel method

LiSn₂P₃O₁₂ with sodium (Na) super ionic conductor (NASICON)-type rhombohedral structure was successfully obtained at low sintering temperature, 600 °C via citric acid-assisted sol-gel method. However, when the sintering temperature increased to 650 °C, triclinic structure coexisted with the rhombohedral structure as confirmed by X-ray diffraction analysis. Conductivity–temperature dependence of all samples were studied using impedance spectroscopy in the temperature range 30 to 500 °C, and bulk, grain boundary and total conductivity increased as the temperature increased. The highest bulk conductivity found was 3.64?×?10^?5 S/cm at 500 °C for LiSn₂P₃O₁₂ sample sintered at 650 °C, and the lowest bulk activation energy at low temperature was 0.008 eV, showing that sintering temperature affect the conductivity value. The voltage stability window for LiSn₂P₃O₁₂ sample sintered at 600 °C at ambient temperature was up to 4.4 V. These results indicated the suitability of the LiSn₂P₃O₁₂ to be exploiting further for potential applications as solid electrolytes in electrochemical devices.     

Structural, AC, and DC magnetic properties of Zn1−xCoxFe2O4

Structural, AC and DC magnetic properties of polycrystalline Zn_1−xCo_xFe₂O₄ (x=0.2, 0.4) samples sintered at various temperatures (1100-1300 °C), and various dwell times (0.2-15 h) have been investigated thoroughly. The bulk density of the Zn_0.60Co_0.40Fe₂O₄ samples increases as the sintering temperature (T_s) increases from 1100 to 1250 °C, and above 1250 °C the bulk density decreases slightly. The Zn_0.80Co_0.20Fe₂O₄ samples show similar behavior of changes to that of Zn_0.60Co_0.40Fe₂O₄ samples except that the bulk density is found to be highest at 1200 °C. The DC magnetization as a function of temperature curves show that the Zn_0.60Co_0.40Fe₂O₄ sample is ferrimagnetic at room temperature while the Zn_0.80Co_0.20Fe₂O₄ sample is paramagnetic at room temperature. The T_c of Zn_0.80Co_0.20Fe₂O₄ sample is found to be 170 K from DC magnetization measurement. Separate measurement (AC magnetization), initial permeability as a function of temperature shows that the T_c of the Zn_0.60Co_0.40Fe₂O₄ sample is 353 K. Slight variation of T_c is observed depending on sintering condition. The initial permeability for the Zn_0.60Co_0.40Fe₂O₄ composition sintered at 1250 °C is found to be maximum.     

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.     

Structural and electrical properties of KCa<Subscript>2</Subscript>Nb<Subscript>5</Subscript>O<Subscript>15</Subscript> ceramics

A polycrystalline sample of KCa₂Nb₅O₁₅ with tungsten bronze structure was prepared by a mixed oxide method at high temperature. A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound shows a uniform grain distribution throughout the surface of the sample. Studies of temperature variation on dielectric response at various frequencies show that the compound has a transition temperature well above the room temperature (i.e., 105°C), which was confirmed by the polarization measurement. Electrical properties of the material have been studied using a complex impedance spectroscopy (CIS) technique in a wide temperature (31–500°C) and frequency (10²–10⁶ Hz) range that showed only bulk contribution and non-Debye type relaxation processes in the material. The activation energy of the compound (calculated from both the loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers. A possible ‘hopping’ mechanism for electrical transport processes in the system is evident from the modulus analysis. A plot of dc conductivity (bulk) with temperature variation demonstrates that the compound exhibits Arrhenius type of electrical conductivity.      

Structural and magnetic properties of bulk and thin films of Mg0.95Mn0.05Fe2O4

We present here a comparative study on structural and magnetic properties of bulk and thin films of Mg_0.95Mn_0.05Fe₂O₄ ferrite deposited on two different substrates using X-ray diffraction (XRD) and dc magnetization measurements. XRD pattern indicates that the bulk sample and their thin films exhibit a polycrystalline single phase cubic spinel structure. It is found that the film deposited on indium tin oxide coated glass (ITO) substrate has smaller grain size than the film deposited on platinum coated silicon (Pt–Si) substrate. Study of magnetization hysteresis loop measurements infer that the bulk sample of Mg_0.95Mn_0.05Fe₂O₄ and its thin film deposited on Pt–Si substrate shows a well-defined hysteresis loop at room temperature, which reflects its ferrimagnetic behavior. However, the film deposited on ITO does not show any hysteresis, which reflects its superparamagnetic behavior at room temperature.     

Spinel cobalt ferrite by complexometric synthesis

Magnetic fine particles of cobalt ferrite (CoFe₂O₄) have been synthesized using complexometric method in which ethylene diamine tetra acetic acid C₁₀H₁₆N₂O₈ (EDTA) acts as a complexing agent. The crystallographic structure, microstructure and magnetic properties of the synthesized powder were characterized by using X-ray diffraction (XRD), particle size analysis and vibrating sample magnetometry (VSM). The material crystallized in cubic spinel structure with lattice parameter of about 8.38 Å. Depending on the calcining temperature, the particle size of the powders varies in the range of hundreds of nanometers to tens of micrometers. A desired relative density above 95% of the theoretical value is obtained for the bulk sample after sintering. The calcined powders and sintered sample exhibit saturation magnetizations around 80 Am²/kg which is expected for inverse CoFe₂O₄. With increasing calcining temperature the coercivity of these samples decreases. This simple synthesis route leads to a reproducible and stoichiometric material.     

Effects of sintering temperature and atmosphere on magnetism in Mn-doped TiO2 bulk samples

Magnetic properties have been investigated on Mn doped TiO₂(Ti_0.98Mn_0.02O₂) bulk samples prepared by solid state reaction, which were sintered at different temperature ranging from 450 ^°C to 900 ^°C in air and argon atmosphere, respectively. The results show that the magnetic properties were strongly dependent on the sintering temperature and atmosphere. For samples sintered in air, the magnetization initially increase with the increase of sintering temperature up to 600 ^°C and thereafter it decrease. While the magnetization of samples sintered in argon atmosphere decreases monotonically with the increase of sintering temperature. Furthermore, for samples sintered at 600 ^°C in air, the magnetic susceptibility exhibits a dominant Curie-Weiss behaviour and no magnetic transition is observed over the temperature range from 10 to 300 K. In contrast, for samples sintered in argon atmosphere, besides the magnetic transition near 45 K perhaps caused by Mn₃O₄, another magnetic transition appears near room temperature.     

氧离子导体La1.9Y0.1Mo2O9细晶粒陶瓷的制备和电学性质研究

采用溶胶凝胶法合成的La_1.9Y_0.1Mo₂O₉纳米晶粉体, 结合微波烧结技术制备出不同晶粒度的La_1.9Y_0.1Mo₂O₉块体样品. 利用X射线衍射仪(XRD)、高分辨透射显微镜(HRTEM)、场扫描显微镜(SEM)对粉体及陶瓷块体的物相、 形貌进行了表征, 利用交流阻抗谱仪测试了样品不同温度下的电导率. 实验结果表明, 掺Y的La_1.9Y_0.1Mo₂O₉能将高温立方β 相稳定到室温; 块体样品致密均匀, 平均晶粒度范围在60 nm–4 μm之间; 致密度高的样品表现出高的电导率, 其中900 ℃烧结样品的电导率600 ℃时高达0.026 S/cm, 比固相反应法制备的La_1.9Y_0.1Mo₂O₉样品高出约1倍. 总结认为样品的致密性对电导率影响较大, 是通过影响晶界电导率来影响总电导率的, 样品的晶粒度(在60 nm–4 μm范围内)对电导率的影响还不能确定. 关键词： 氧离子导体 1.9Y_0.1Mo₂O₉')" href="#">La_1.9Y_0.1Mo₂O₉ 细晶粒陶瓷 微波烧结     

Li2B4O7晶体的晶格振动光谱

在室温下测量了Li₂B₄O₇单晶的各种振动类的偏振Raman散射谱和该晶体粉末样品的红外吸收谱(200—4000cm^-1)。根据LO-TO劈裂的实验结果,计算出该晶体极化模的有效电荷和振子强度。通过与BBO和LBO晶体的结构和B—O伸缩振动模频率比较,得出:Li₂B₄O₇晶体可能有较大的非线性光学系数。 关键词：     

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.     

Effect of Co 2 + content on the magnetic properties of Co x Fe 3 − x O 4 /SiO 2 nanocomposites

Non-stoichiometric Co_xFe_3???xO₄/SiO₂ (x = 0.8, 0.9, 1.0, 1.1) nanocomposites have been prepared by sol-gel method. The structure, morphology and magnetic properties of the obtained samples were characterized by X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and Mössbauer spectroscopy at room temperature. As the Co^2?+? content increases, the average particle size of the spherical Co_xFe_3???xO₄ in the samples decreases and the lattice constants increases. The hyperfine fields for both A- and B-site decrease, while the fraction of Co^2?+? occupying the A-site increases. Magnetization measurements show the saturation magnetization and coercivity of Co_xFe_3???xO₄/SiO₂ decrease with increasing Co^2?+? content. The decrease in magnetization results from the weakened A-B interactions between Fe^3?+?, and the change in coercivity can be related to the variation of Co^2?+? at B-site and the decreasing particle size.     

Mössbauer and magnetic studies on nanocrystalline NiFe2O4 particles prepared by ethylene glycol route

NiFe₂O₄ nanoparticles have been synthesized by co-precipitation method at 145°C in N₂ atmosphere using ethylene glycol as solvent and capping agent. This gives the promising synthesis route for nanoparticles at low temperature. The as-synthesized NiFe₂O₄ is subsequently heated at 400°C, 500°C, 700°C and 800°C. Crystallite size increases with the heat treatment temperature. The heat treatment temperature has direct effect on the electron paramagnetic resonance and intrinsic magnetic properties. The room temperature Mössbauer spectrum of the 800°C heated sample shows the two sextets pattern indicating that the sample is ferrimagnetic and Fe^3?+? ions occupy both tetrahedral and octahedral sites of spinel structure.     

Mössbauer effect studies on the formation of iron oxide phases synthesized via microwave–hydrothermal route

Microwave–hydrothermal (MH) route was employed to synthesize various iron oxide phases in ultra-fine crystalline powders by using ferrous sulphate and sodium hydroxide as starting chemicals. All chemical reactions were carried out under identical MH conditions, namely, at 190°C, 154 psi, 30 min, by varying the molar ratio (MR) of FeSO₄/NaOH in the aqueous solutions. The variation of MR has a dramatic effect on the crystallization behavior of various phases of iron oxides under MH processing conditions. For example, spherical agglomerates of Fe₃O₄ powder were obtained if MR equal to 0.133 (pH?>?10 sample A). On the other hand non-stoichiometric Fe₃O₄ powders (Sample B) were obtained for all higher MR of FeSO₄/NaOH between 0.133 and 4.00 (6.6?2O₃ powders (sample C) were produced. Fe⁵⁷ Mössbauer spectra were recorded for all the three sets of samples at room temperature. In the case of sample B, temperature dependent Mössbauer spectra were recorded in the range of 77–300 K to understand the non-stoichiometric nature of Fe₃O₄ powders. All these results are discussed in the present paper.     

Structural and impedance properties of Ca3Nb2O8 ceramics

Polycrystalline sample of Ca₃Nb₂O₈ was prepared by a high-temperature solid-state reaction technique. X-ray diffraction (XRD) analysis confirms the formation of single-phase compound of hexagonal (rhombohedral) crystal structure at room temperature. Scanning electron micrograph of the material showed uniform grain distribution on the surface of the sample. Detailed studies of dielectric properties of the compound, studied in a wide frequency range (10²-10⁶ Hz) at different temperatures (25-500 °C), exhibit a dielectric anomaly suggesting phase transition of ferroelectric-paraelectric and structural type at 300 °C. Electrical properties of the material were analyzed using a complex impedance technique. The Nyquists plot showed the presence of bulk effect in the material in the studied temperature range. Studies of electrical conductivity over a wide temperature range suggest that the compound has negative temperature coefficient of resistance behavior.     

Magnetic and Mössbauer studies on nanocrystalline Co1−x Li x Fe2O4 (x = 0, 0.2)

Ultrafine particles of Co_1???x Li _x Fe₂O₄ (x?= 0, 0.2) samples are prepared by glycine–nitrate combustion route. X-ray diffraction and transmission electron microscopy studies show that the samples have cubic spinel structure and average crystallite sizes of x?= 0 and 0.2 are 36 and 44 nm respectively. Vibrating sample magnetometer studies revealed the ferromagnetic nature of the samples. Li-doped CoFe₂O₄ sample showed higher values of coercive field, remanent magnetization and saturation magnetization compared to pure CoF₂O₄ indicating the enhancement of magnetic interactions. Mössbauer spectra at 77 K exhibited two broad sextets indicating that Fe^3?+? ions occupy both tetrahedral and octahedral sites. From these studies, it is concluded that Co_1???x Li _x Fe₂O₄ (x?= 0, 0.2) samples exhibit an inverse spinel structure. At room temperature, two sextets are superimposed on a very broad non-Lorentzian background indicating the presence of superparamgnetic fraction in agreement with the microscopic observations.     

High temperature study of yttrium--barium--copper oxides near the YBa2Cu3Ox composition by 111In/Cd time differential \gamma--\gamma perturbed angular correlation spectroscopy

The local atomic order around very dilute indium impurities in c-axis-oriented YBa₂Cu₃O₇ and YBa₂Cu₃O_6.25 films at room temperature and in YBa₂Cu₃O_x bulk powders held in air or oxygen over a wide temperature range were investigated using ¹¹¹In/Cd \gamma--\gamma perturbed angular correlation (PAC) spectroscopy. The probe atoms occupy a single substitutional lattice position in YBa₂Cu₃O_x, and evidence reported here strongly supports previous claims that this is the yttrium position. In YBa₂Cu₃O_x powders, the local atomic order changes continuously with temperature. At room temperature the electric field gradient measured by PAC in bulk YBa₂Cu₃O_x powder is indistinguishable from that in the fully oxygenated YBa₂Cu₃O₇ film. Near the decomposition temperature, the bulk YBa₂Cu₃O_x powder data are semiquantitatively similar to data in the room temperature YBa₂Cu₃O_6.25 film, with quantitative differences that we attribute to temperature averaging in the former. Other sites usually found in PAC spectra of YBa₂Cu₃O_x bulk samples arise from ¹¹¹In dissolved in Y₂BaCuO₅ and Y₂Cu₂O₅ impurity phases. The latter phase apparently arises because of significant barium loss during processing; the barium deficiency is clearly demonstrated by comparison of PAC data with the alloy phase diagram above the decomposition temperature. PAC data on pure Y₂Cu₂O₅ are reported here also. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of synthesis method on structural and magnetic properties of cobalt ferrite nanoparticles

The Co–ferrite nanoparticles having a relatively uniform size distribution around 8 nm were synthesized by three different methods. A simple co-precipitation from aqueous solutions and a co-precipitation in an environment of microemulsions are low temperature methods (50 °C), whereas a thermal decomposition of organo-metallic complexes was performed at elevated temperature of 290 °C. The X-ray diffractometry (XRD) showed spinel structure, and the high-resolution transmission electron microscopy (HRTEM) a good crystallinity of all the nanoparticles. Energy-dispersive X-ray spectroscopy (EDS) showed the composition close to stoichiometric (~CoFe₂O₄) for both co-precipitated nanoparticles, whereas the nanoparticles prepared by the thermal decomposition were Co-deficient (~Co_0.6Fe_2.4O₄). The X-ray absorption near-edge structure (XANES) analysis showed Co valence of 2+ in all the samples, Fe valence 3+ in both co-precipitated samples, but average Fe valence of 2.7+ in the sample synthesized by thermal decomposition. The variations in cation distribution within the spinel lattice were observed by structural refinement of X-ray absorption fine structure (EXAFS). Like the bulk CoFe₂O₄, the nanoparticles synthesized at elevated temperature using thermal decomposition displayed inverse spinel structure with the Co ions occupying predominantly octahedral lattice sites, whereas co-precipitated samples showed considerable proportion of cobalt ions occupying tetrahedral sites (nearly 1/3 for the nanoparticles synthesized by co-precipitation from aqueous solutions and almost 1/4 for the nanoparticles synthesized in microemulsions). Magnetic measurements performed at room temperature and at 10 K were in good agreement with the nanoparticles’ composition and the cation distribution in their structure. The presented study clearly shows that the distribution of the cations within the spinel lattice of the ferrite nanoparticles, and consequently their magnetic properties are strongly affected by the synthesis method used.     

Induced crystallization and the physical properties of PbO–Sb2O3–As2O3: MoO3 glass system

PbO–Sb₂O₃–As₂O₃ glasses mixed with different concentrations of MoO₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. The X-ray diffraction and the scanning electron microscopic studies have revealed the presence of Pb₅Sb₂O₈, PbSb₂O₆, SbAsO₄, Sb₂MoO₆, Sb₄Mo₁₀O₃₁, As₄Mo₃O₁₅, Pb₅Sb₄O₁₁ crystalline phases in these samples. The differential thermal analysis indicated that the surface crystallization prevails over the bulk crystallization as the concentration of the crystallizing agent is increased. The infrared (IR) spectral studies exhibit bands due to MoO₄ structural units in addition to the conventional bands due to various antimonate and arsenate structural groups. The studies on PbO–Sb₂O₃–As₂O₃: MoO₃ glass-ceramics with respect to various physical properties viz., dielectric properties over a range of frequency and temperature, optical absorption, electron spin resonance (ESR) and magnetic susceptibility at room temperature have also been reported. The optical absorption, ESR and magnetic susceptibility studies indicated that the molybdenum ions exist in Mo⁵⁺ state in addition to Mo⁶⁺ state in these samples. The redox ratio found to increase as the concentration of the MoO₃ is increased. The variations observed in all these properties with the concentration of the crystallizing agent have been analyzed in the light of different oxidation states and environment of molybdenum ions in the glass ceramic network.     

Induction heating studies of magnetite nanospheres synthesized at room temperature for magnetic hyperthermia

An investigation of the synthesis of Fe₃O₄ nanopowders by the co-precipitation method is reported from aqueous and ethanol mediums. X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer are utilized to study the effect of variation of synthesis conditions on the crystal structure, crystallite size, microstructure and magnetic properties of the formed powders. The XRD analysis showed that the crystalline Fe₃O₄ phase was formed at Fe³⁺/Fe²⁺ molar ratio 2.0 prepared at room temperature for 1 h at pH 10. The crystallite size was in the range between 8 and 11 nm. TEM micrographs showed that the particles appeared as nanospheres. Superparamagnetic nanoparticles with low coercivity and remanence magnetization were achieved. Heating properties of the nanosphere samples in an alternating magnetic field at 160 KHz were evaluated. An excellent heating efficiency for the sample prepared in ethanol medium is a result of more relaxation losses occurring due to its small particle size.