Direct synthesis and characterization of mesoporous Fe3O4 through pyrolysis of ferric nitrate-ethylene glycol gel

Mesoporous magnetite (Fe₃O₄) was successfully synthesized on a large scale by direct pyrolysis of ferric nitrate-EG (EG = ethylene glycol) gel in a one-end closed horizontal tube furnace in the air without using any template, additions, and carrier gas. The as-synthesized mesoporous Fe₃O₄ were characterized by powder X-ray diffraction (XRD), infrared spectra (IR), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), and thermal gravimetric analysis (TGA). Results from TEM showed that the as-obtained Fe₃O₄ has mesoporous structure formed by the loose agglomeration of nanoparticles with diameter of about 6 nm, which was also confirmed by small-angle XRD and nitrogen adsorption analysis. Furthermore, vibrating sample magnetometer (VSM) measurements indicated that the saturated magnetization of the as-obtained mesoporous Fe₃O₄ was ferromagnetic with the saturation magnetization (Ms) and coercivity (Hc) of 46 emu/g and 136 Oe, respectively. In addition, a possible growth mechanism of mesoporous Fe₃O₄ was also discussed.     

Hydrothermal growth and characterization of magnetite (Fe3O4) thin films

Well-crystallized magnetite (Fe₃O₄) thin films were successfully prepared by a simple hydrothermal process using hydrazine hydrate as the mineralizer. X-ray diffraction and scanning electron microscopy (SEM) and transmission electron microscopy were employed to characterize the products. SEM images show that the uniform Fe₃O₄ film (∼ 3 μm in thickness) is firmly grown on a nickel substrate. The magnetic property of the Fe₃O₄ particles scraped from the film was measured by Physical Property Measurement System (PPMS) at room temperature, and the magnetization curve reveals a soft ferromagnetic behavior with high saturation magnetization of 85 emu/g. Furthermore, the chemical and growth mechanisms for the hydrothermal formation of the Fe₃O₄ film are discussed.     

Low temperature synthesis of Fe3O4 micro-spheres and its application in lithium ion battery

Fe₃O₄ micro-spheres with nanoparticles close-packed architectures were synthesized via a simple chemical method using (NH₄)₂Fe(SO₄)₂·6H₂O, hexamethylenetetramine, and NaF as reaction materials. This chemical synthesis took place in a vitreous jar under low temperature (90 °C) and atmospheric pressure. The morphology and structure of the as-synthesized products were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and Raman spectrum. Electrochemical properties of the as-synthesized Fe₃O₄ micro-spheres as anode electrode of lithium ion batteries were studied by conventional charge/discharge tests, which exhibit steady charge/discharge platforms at different current densities. The as-prepared Fe₃O₄ electrode shows high initial discharge capacity of 1166 and 1082 mAh g⁻¹ at current density of 0.05 and 0.1 mA cm⁻², respectively.     

Fe2O4催化纤维素水热法制备 Fe2O3/ 碳纳米复合材料

目的在较为温和的条件下制备氧化铁/碳纳米复合材料。方法以纳米Fe3O4粉体为催化剂,水热催化纤维素碳化,并借助扫描电镜、透射电镜、X射线光电子能谱仪和X射线衍射仪对碳化产物进行表征分析。结果获得了粒径约为150 nm的枣核形氧化铁/碳纳米复合材料。结论通过相对温和的水热反应,纤维素被碳化形成了壳核结构的纳米产物,Fe3O4催化剂在反应过程中被氧化并成为壳核结构产物的核心。     

Preparation and characteristics of Fe3O4@YVO4:Eu bifunctional magnetic-luminescent nanocomposites

A facile direct precipitation method has been developed for the synthesis of bifunctional magnetic-luminescent nanocomposites with Fe₃O₄ nanoparticles as the core and YVO₄:Eu³⁺ as the shell. Transmission electron microscopy (TEM) images revealed that the obtained bifunctional nanocomposites had a core-shell structure and a spherical morphology. The average size was ∼150 nm, and the thickness of the shell was ∼15 nm. The X-ray diffraction (XRD) patterns showed that a cubic spinel structure of Fe₃O₄ core and a tetragonal phase of YVO₄ shell were obtained. Fourier transform infrared (FT-IR) spectra confirmed that the YVO₄:Eu³⁺ had been successfully deposited on the surface of Fe₃O₄ nanoparticles. Photoluminescence (PL) spectra indicated that the nanocomposites displayed a strong red characteristic emission of Eu³⁺. Magnetic measurements showed that the obtained bifunctional nanocomposites exhibited superparamagnetic behavior at room temperature. Therefore, the bifunctional nanocomposites are expected to develop many potential applications in biomedical fields.     

Polishing properties of tiny grinding wheel based on Fe3O4 electrorheological fluid

Experiments were conducted to reveal the polishing properties of the Fe₃O₄ electrorheological fluid, which was used to form a dynamical, instantaneous tiny grinding wheel to polish optical glass. The profile of the polished area of the glass surface indicates that the material removal process is dominated by the synergy of the applied pressure and the relative velocity between the abrasives and the workpiece to be polished. It is also found that the rate of material removal is proportional to the intensity of external electric field and decreases with the extension of the machining gap between the workpiece and the needle-like tool.     

Photocatalytic performance of nano-photocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis

Nano-particles of homogeneous solid solution between TiO₂ and Fe₂O₃ (up to 10 mol%) have been prepared by mechanochemical milling of TiO₂ and yellow Fe₂O₃/red Fe₂O₃/precipitated Fe (OH)₃ using a planetary ball mill. Such novel solid solution cannot be prepared by conventional co-precipitation technique. A preliminary investigation of photocatalytic activity of mixed oxide (TiO₂/Fe₂O₃) on photo-oxidation of different organic dyes like Rhodamine B (RB), Methyl orange (MO), Thymol blue (TB) and Bromocresol green (BG) under visible light (300-W Xe lamp; λ > 420 nm) showed that TiO₂ having 5 mol% of Fe₂O₃ (YFT1) is 3-5 times higher photoactive than that of P25 TiO₂. The XRD result did not show the peaks assigned to the Fe components (for example Fe₂O₃, Fe₃O₄, FeO₃, and Fe metal) on the external surface of the anatase structure in the Fe₂O₃/TiO₂ attained through mechanochemical treatment. This meant that Fe components were well incorporated into the TiO₂ anatase structure. The average crystallite size and particle size of YFT1 were found to be 12 nm and 30 ± 5 nm respectively measured from XRD and TEM conforming to nanodimensions. Together with the Fe component, they absorbed wavelength of above 387 nm. The band slightly shifted to the right without tail broadness, which was the UV absorption of Fe oxide in the Fe₂O₃/TiO₂ particle attained through mechanochemical method. This meant that Fe components were well inserted into the framework of the TiO₂ anatase structure. EPR and magnetic susceptibility show that Fe³⁺ is in low spin state corresponding to μ_B = 1.8 BM. The temperature variation of μ_B shows that Fe³⁺ is well separated from each other and does not have any antiferromagnetic or ferromagnetic interaction. The evidence of Fe³⁺ in TiO₂/Fe₂O₃ alloy is also proved by a new method that is redox titration which is again support by the XPS spectrum.     

Facile synthesis, magnetic and microwave absorption properties of Fe3O4/polypyrrole core/shell nanocomposite

Fe₃O₄/polypyrrole (PPy) core/shell nanocomposite, with Fe₃O₄ nanoparticle as core and PPy as shell, could be facilely synthesized via in situ chemical oxidative polymerization of pyrrole monomers on the surface of Fe₃O₄ nanoparticles. The results indicate that core/shell nanocomposite consists of Fe₃O₄ core with the mean diameter of 100 nm and adjacent PPy shell with a thickness of about 70 nm. The as-prepared Fe₃O₄/PPy core/shell nanocomposite exhibits a saturated magnetization of 20.1 emu/g and coercivity value of 368.3 Oe, respectively. The electromagnetic characteristics of Fe₃O₄/PPy core/shell nanocomposite were also investigated with a vector network analyzer in the 2-18 GHz range. The absorbing peak position moves to lower frequency with increasing the thicknesses of samples. The value of the minimum reflection loss is −22.4 dB at 12.9 GHz for Fe₃O₄/PPy core/shell nanocomposite with a thickness of 2.3 mm, and a broad peak with a bandwidth lower than −10 dB is about 5 GHz. Such strong absorption is attributed to better electromagnetic matching due to the existence of PPy and the special core/shell structure.     

One-step solvothermal approach for preparing soft magnetic hydrophilic PFR coated Fe3O4 nanocrystals

The hydrophilic phenol formaldehyde resin coated Fe₃O₄ nanocrystals are prepared via a novel one-step solvothermal approach at 160 °C for 6-9 h without inert gas protection. Water-glycol mixture is used as solvent in common air surrounding. FeSO₄·7H₂O, hexamethylenetetramine and phenol are used as resource materials without any others additives or surfactants. The transmission electronic microscope images show the samples are composed of sphere-like particles with sizes about 10-20 nm. The X-ray diffraction data indicate cube-phase Fe₃O₄ nanocrystals are obtained at given conditions. Fourier transform infrared spectra further reveal the samples are consisted of Fe₃O₄ and PFR. Without modified pH and added surfactants, the solubility of the obtained sample is over 1% in water, which is far more than its solubility in toluene. Room-temperature hysteresis loop indicate that the as-obtained nano-crystals possess soft magnetic properties with high saturated mass magnetization (50.6 emu/g) and negligible coercivity.     

Electromagnetic composite films based on polypyrrole hydro-sponge and Fe3O4 ferrofluid

The preparation of free-standing electromagnetic composite films based on conductive polypyrrole (PPy) hydro-sponge and the Fe₃O₄ ferrofluid have been successfully accomplished via self-assembly in the presence of β-cyclodextrin sulfate and under static condition. Transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction (XRD) are used to study the morphology of the PPy-Fe₃O₄ composite. Structural characterizations by Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) have proved the interactions between Fe₃O₄ and PPy chains. As-prepared films possess high electrical conductivity, remarkable magnetic response as well as appropriate flexility. Both the conductivity and magnetization of the composite, the latter in particular, depend strongly on the Fe₃O₄ content and thus can be optimized by adjusting the relative content of Fe₃O₄ in the composite. The combination of both magnetic and conducting activities of the resulting composite makes it be a potential candidate as functional material in electromagnetic devices, such as magnetic-controlled switches.     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

In situ synthesis and characterization of polyaniline–CaCu3Ti4O12 nanocrystal composites

High dielectric constant (ca. 2.4 × 10⁶ at 1 kHz) nanocomposite of polyaniline (PANI)/CaCu₃Ti₄O₁₂ (CCTO) was synthesized using a simple procedure involving in situ polymerization of aniline in dil. HCl. The PANI and the composite were subjected to X-ray diffraction, Fourier transform infrared, thermo gravimetric, scanning electron microscopy and transmission electron microscopy analyses. The presence of the nanocrystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. Frequency dependent characteristics of the dielectric constant, dielectric loss and AC conductivity were studied for the PANI and the composites. The dielectric constant increased as the CCTO content increased in PANI but decreased with increasing frequency (100 Hz–1 MHz) of measurement. The dielectric loss was two times less than the value obtained for pure PANI around 100 Hz. The AC conductivity increased slightly up to 2 kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers.     

Solvothermal synthesis and characterization of size-controlled Fe3O4 nanoparticles

Size-controlled Fe₃O₄ nanoparticles were prepared via a facile solvothermal method by using the mixed surfactants of SDS and PEG as protective reagents. The sizes of the nanoparticles can be varied from 15 to 190 nm by adjusting the experimental conditions. The influences of the protective reagents, reaction time, the initial concentration of the reactant, molar ratio of FeCl₃ and protective reagents on the size of the produced nanoparticles were studied. The size and morphology of the products were investigated in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and scanning electron microscopy (SEM).     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

Ethanol-assisted synthesis of Zn0.5Fe2.5O4 nanocrystals in thermal solvent of paraffin

In the atmosphere of N₂, low cost paraffin slices were refined and then successfully utilized as a solvent instead of the expensive high-carbon alkanes or alkenes like 1-octadecene to synthesize Zn_0.5Fe_2.5O₄ nanocrystals at 320 °C. In the experiments, the precursor solutions of ferric and zinc oleates were stoichiometrically prepared and injected by two-step operations into the hot solvent, together with controlled amounts of ethanol to tailor their thermal decomposition performances. The synthesized Zn_0.5Fe_2.5O₄ nanocrystals were characterized by XRD and FESEM, having uniform morphology and a quasi-monodisperse size distribution with a mean value 25 nm and a standard deviation of ±12.3%. The formation and structural characteristics of Zn_0.5Fe_2.5O₄ nanocrystals are attributed to the catalysing function of ethanol and the effective separation of nucleation and growth of nanocrystals via the two-step injections of reactive precursors.     

Luminescent and magnetic properties of YVO4:Ln@Fe3O4 (Ln = Eu or Dy) nanocomposites

A series of core-shell bifunctional magnetic-optical YVO₄:Ln³⁺@Fe₃O₄ (Ln³⁺ = Eu³⁺ or Dy³⁺) nanocomposites have been successfully synthesized via two-step method. The nanocomposites have the advantage of high magnetic responsive and unique luminescence properties. The structure, luminescent and magnetic properties of the nanocomposites were investigated by XRD, TEM, PL and VSM. The maximum emission peaks of the nanocomposites are at 618 nm (doping Eu³⁺), 574 nm (doping Dy³⁺). The special saturation magnetization of the nanocomposites is 54 emu/g. The diameter of the nanocomposites is 400-900 nm.     

Influence of MnO2 on the sintering behavior and magnetic properties of NiFe2O4 ferrite ceramics

The samples with small amounts of MnO₂ (0, 0.5, 1.0, 1.5, 2.0, and 2.5 wt%, respectively) were prepared via ball-milling process and two-step sintering process from commercial powders (i.e. Fe₂O₃, NiO and MnO₂). Microstructural features, phase transformation, sintering behavior and magnetic properties of Mn-doped NiFe₂O₄ composite ceramics have been investigated by means of scanning electron microscopy (SEM), differential thermal analyzer, X-ray diffraction (XRD), thermal dilatometer and vibrating sample magnetometer (VSM) respectively. The XRD analysis and the result of differential thermal analysis indicate that the reduction of MnO₂ into Mn₂O₃ and the following reduction of Mn₂O₃ into MnO existed in sintering process. No new phases are detected in the ceramic matrix, the crystalline structure of the ceramic matrix is still NiFe₂O₄ spinel structure. Morphology and the detecting result of thermal dilatometer show that MnO₂ can promote the sintering process, the temperature for 1 wt% MnO₂-doped samples to reach the maximum shrinkage rate is 59 °C lower than that of un-doped samples. For 1 wt% MnO₂-doped samples, the value of the saturation magnetization (M_s) and coercivity (H_c) is 15.673 emu/g and 48.316 Oe respectively.     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料,通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD),场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明,Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构,包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善,1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1,充放电循环500次后容量保持率分别为88.4%和78.2%,而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1,500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1,而未包覆材料的活化能为36.24 kJ?mol-1,包覆有效降低了材料Li+扩散所需克服的能垒,提高了材料的电化学性能。