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1.
In this work, the effect of nickel doping on the structural and magnetic properties of Fe3O4 nanoparticles is analysed. Ni(x)Fe(3-x)O4 nanoparticles (x = 0, 0.04, 0.06 and 0.11) were obtained by chemical co-precipitation method, starting from a mixture of FeCl2 x 4H2O and Ni(AcO)2 x 4H2O salts. The analysis of the structure and composition of the synthesized nanoparticles confirms their nanometer size (main sizes around 10 nm) and the inclusion of the Ni atoms in the characteristic spinel structure of the magnetite Fe3O4 phase. In order to characterize in detail the structure of the samples, X-ray absorption (XANES) measurements were performed on the Ni and Fe K-edges. The results indicate the oxidation of the Ni atoms to the 2+ state and the location of the Ni2+ cations in the Fe2+ octahedral sites. With respect to the magnetic properties, the samples display the characteristic superparamagnetic behaviour, with anhysteretic magnetic response at room temperature. The estimated magnetic moment confirms the partial substitution of the Fe2+ cations by Ni2+ atoms in the octahedral sites of the spinel structure.  相似文献   

2.
Pure and mixed cobalt copper ferrites are of great interest due to their widespread application in electronics and medicine. We report on the electronic structure of a nanoferrite Cu(x)Co(1-x)Fe2O4 (0.0 < or = x < or = 1.0) system studied by X-ray absorption spectroscopy. These magnetic nanoferrites (average crystallite size approximately 31-43 nm) were synthesized by an auto combustion method and are characterized by high resolution X-ray diffraction and near edge X-ray absorption fine structure measurements at the O K and Co, Cu, and Fe L-edges. The O K-edge spectra suggest that there is a strong hybridization between O 2p and 3d electrons of Co, Cu and Fe cations and Fe L3,2-edge spectra indicate that Fe ions coexist in mixed valence states (Fe3+ and Fe2+) at tetrahedral and octahedral sites of the spinel structure. Copper and cobalt ions are distributed in the divalent state in octahedral sites of the spinel structure. The origin of high saturation magnetization and coercivity in cobalt-copper ferrites are explained in light of these results.  相似文献   

3.
The structural and magnetic properties of Co(1-x)Zn(x)Fe2O4 ferrites (Co-Zn ferrites) are investigated in a narrow compositional range around x = 0.6, which is of interest because of applications in magnetic fluid hyperthermia. The study by x-ray and neutron diffraction, M?ssbauer spectroscopy and magnetization measurements is done on nanoparticles prepared by the coprecipitation method and bulk samples sintered at high temperatures. In spite of the known preference of Zn2+ for tetrahedral (A) sites and Co2+ for octahedral [B] sites, the cations are distributed nearly evenly over the two sites of spinel structure and there is also a variable number of [B] site vacancies (see text), making cobalt ions trivalent. In particular for x = 0.6, the cationic distribution is refined to [Formula: see text] and [Formula: see text] for the 13 nm particles (T(C) = 335 K) and bulk sample (T(C) = 351 K), respectively.  相似文献   

4.
Both structural refinement using X-ray powder diffraction data and energy calculation using quantum mechanics were used to determine the site preference and the amount of Gd in the host lattice of Gd doped Fe3O4 [Gd(x)Fe(3-x)O4 (x = 0.1)] nanopowder prepared by the sonochemical method. Among possible cation-disorder models, the model proposed by structural refinement, in which Gd ions might preferentially occupy the octahedral sites in Gd doped Fe3O4 having the inverse spinel structure, was confirmed by geometry energy calculation using a first-principle based on the density-functional theory. The final converged weighted R-factor, R(wp), and the goodness-of-fit indicator, S (= R(wp)/R(e)) were 6.73% and 1.22, respectively. The occupancy of Gd ions occupying octahedral sites was 0.04(2).  相似文献   

5.
The dense ceramic membranes BaCo(0.7)Fe(0.2)Nb(0.1)O(3-δ) (BCFN) combined with GdBaCo(2-x)Fe(x)O(5+δ) (0 ≤ x ≤ 2.0) surface modification layers was investigated for hydrogen production by partial oxidation reforming of coke oven gas (COG). As oxygen permeation of BCFN membrane is controlled by the rate surface exchange kinetics, the GdBaCo(2-x)Fe(x)O(5+δ) materials improve the oxygen permeation flux of the BCFN membrane by 20-44% under helium atmosphere at 750 °C. The maximum oxygen permeation flux reached 14.4 mL min(-1) cm(-2) in the GdBaCoFeO(5+δ) coated BCFN membrane reactor at 850 °C, and a CH(4) conversion of 94.9%, a H(2) selectivity of 88.9%, and a CO selectivity of 99.6% have been achieved. The GdBaCo(2-x)Fe(x)O(5+δ) coating materials possess uniform porous structure, fast oxygen desorption rate and good compatibility with the membrane, which showed a potential application for the surface modification of the membrane reactor.  相似文献   

6.
The purpose of this work was to study the feasibility at laboratory-scale of a new hydrometallurgical process for treating electric arc furnace dusts (EAFD). The proposed process is intended to extract zinc and lead from EAFD without destroying the iron oxides matrix. So, this material can be recycled by the steel industry. Independently of the origin of the samples, major mineralogical forms present in these wastes are Fe3O4, ZnO, ZnFe2O4 and PbOHCl. The proposed process consists of a hydrometallurgical treatment of wastes based on selective leaching of zinc and lead. Initially, a leaching is carried out utilizing a chelating agent, nitrilotriacetate anion (NTA3-), as the protonated form HNTA2-. Treatment of five EAFD samples for an hour at room temperature with a molar solution of reagent results in total leaching of the ZnO. In all cases the solubilized iron does not exceed 3 wt.%. The recovery of zinc and lead is performed by precipitation of metallic sulfides with a solution of Na2S4 sodium tetrasulfide 2M. These metallic sulfides can be used as metallurgical raw materials and the chelating reagent can be reused in the process after pH adjustment. The results of the normalized leaching test AFNOR X31-210 conducted on the leaching residues, shows that all the samples meet acceptance thresholds for hazardous wastes landfill. However, the residues contain a considerable amount of zinc as ZnFe2O4. The extraction of the zinc element requires the destruction of the ferrite structure. In this process, ZnFe2O4 is treated by FeCl3.6H2O. The reaction consists in a particle O2-/Cl- exchange allowing the recovery of zinc as ZnCl2 and iron as hematite Fe2O3. The separation of these products is accomplished by simple aqueous leaching. All of the zinc is extracted in a 8h treatment at 150 degrees C with a molar ratio FeCl3.6H2O/ZnFe2O4 equal to 10. Ultimate solid residues, which have been concentrated in iron, can be oriented towards the steel industry.  相似文献   

7.
Rationally designing active and durable catalysts for the oxygen evolution reaction (OER) is of primary importance in water splitting. Perovskite oxides (ABO3) with versatile structures and multiple physicochemical properties have triggered considerable interest in the OER. The leaching of A site cations can create nanostructures and amorphous motifs on the perovskite matrix, thus facilitating the OER process. However, selectively dissolving A site cations and simultaneously obtaining more active amorphous motifs derived from the B site cations remains a great challenge. Herein, a top‐down strategy is proposed to transform bulk crystalline perovskite (LaNiO3) into a nanostructured amorphous hydroxide by FeCl3 post‐treatment, resulting in an extremely low overpotential of 189 mV at 10 mA cm?2. The top‐down‐constructed amorphous catalyst with a large surface area has dual NiFe active sites, where high‐valence Ni3+‐based edge‐sharing octahedral frameworks are surrounded by interstitial distorted Fe octahedra and contribute to the superior OER performance. This top‐down strategy provides a valid way to design novel perovskite‐derived catalysts.  相似文献   

8.
《Zeolites》1994,14(6):462-468
U.v.-vis-n.i.r. spectroscopy was used to identify the consecutive formation of hydrated octahedral, tetrahedral monoaquo, and trigonal bare Fe(II) species during the dehydration of Fe(II)-A zeolite. The amount of residual water was determined simultaneously using near-infrared water vibration bands. The adsorption of NO probe molecules proved the accessibility of the surface trigonal iron sites. The resulting optical spectrum indicated the formation of a mononitrosyl [Fe(I)-NO+] complex. Upon contact with O2 at 700 K, the ferrous ions of Fe(II)-A were oxidized to ferric species, consuming about one oxygen atom per two iron cations. Upon subsequent reduction with H2, CH4, or CO at 600–700 K, most of the Fe cations were reduced back to surface trigonal Fe(II) species, while a smaller fraction was converted to amorphous ferrous species. These amorphous oxidic species exhibited a higher redox activity than that of the surface trigonal Fe cations.  相似文献   

9.
Planar sensor of SrTi(1-x)Fe(x)O3-delta, x = 0.4 and 0.6, with perovskite structure was fabricated on alumina substrate using thick film technology. Electrical resistance was measured as a function of thermal treatment conditions, atmosphere, time and temperature. Sensing property was also measured as a function of temperature and the gases of O2, CH4, CO, CO2, NO and NO2. The resistance of SrTi(1-x)Fe(x)O3-delta is lower than those of SrTiO3 or SrFeO3. TCR (temperature coefficient of resistance) of zero over 550 degrees C was measured for the composition of SrTi(1-x)Fe(x)O3-delta after thermal treatment at 1100 degrees C in air atmosphere only. The perovskite SrTi(1-x)Fe(x)O3-delta didn't show any response to CH4, CO, CO2, NO and NO2, but an excellent response and recovery characteristics with oxygen concentration.  相似文献   

10.
在干法室温条件下,利用滚压振动磨将金属锌制备成粒度大约40nm的锌粉,用化学共沉淀法制备粒度为10nm左右的Fe3O4。利用Zn-Fe3O4水解系统制备纳米ZnFe2O4,当温度达到300℃后,XRD图上明显出现ZnFe2O4的各个衍射峰,由透射电子显微镜可知,300℃和320℃时得到的纳米粒子都在20nm左右。分别用电子衍射、高分辨电镜对两个样品进行了表征。在距离6cm的30W紫外灯照射下,光催化降解苯酚的实验表明光催化降解的效率顺序为:ZnFe2O4-ZnO-Fe2O3>ZnO-Fe2O3>ZnFe2O4>ZnO>Fe2O3。  相似文献   

11.
1. IntroductionTellurite-borate vitreous systems[1] and binajry tellurite oxide systems containing transition metal ions[2]were investigated in detail due to their interestingproperties having a number of applications in microelectronics. They are optical glajsses with high refraction index (n>2) and a good iR transmission,being suitable as laser and opto-acoustical materials. Tellurite systems containing FeZO3 were studied to reveal their electrical properties as well asthe structural onesl…  相似文献   

12.
The ferrites of Cuo-ZnO-Fe2o3 solid solution series near the molar ratio of ZnxCu1-x were prepared by direct heating of their coprecipitated hydroxides using NH4OH as precipitating agent where x=0.0, 0.2, 0.5, 0.8 and 1.0. Additional amounts of Cu and Zn sulphates were added to compensate the loss during the coprecipitation of the hydroxides. The ferritized samples were characterized by chemical analysis, XRD. DTA, TGA and SEM. XRD of both Zn0.2Cu0.8Fe2O4 and Zn0.5Cu0.5 Fe2O4 that indicates the formation of a heterogeneous ferrite material of ZnFe2O4 and CuFe2O4 mixed with variable amounts of α-Fe2O3. Zn and Cu ferrites were observed only in Zn0.8Cu0.2Fe2O4.From TGA-time relation, the activation energy of the different transformation phases were calculated. It is found that, the activation energy of ZnFe2O4 is slightly equal to 3/2 of that for CuFe2O4. Dielectric measurements show that the electrical behaviour depends on the ordering and disordering of the phases.  相似文献   

13.
La2O3-CeO2 nanopowders with different La2O3 (0-20 mol%) were prepared by the sol-gel method. The modification of the cubic structure of ceria by substituting La3+ for Ce4+ into the lattice of CeO2 has been investigated. The crystal structure of La2O3-CeO2 nanomaterials has been examined by X-ray powder diffraction and analyzed by the Rietveld refinement method. The introduction of La3+ enlarges the octahedral void of unit cell in the cubic CeO2, which favors the oxygen migration in the crystal lattice. Raman characterization results show that the wavenumber of the La2O3-CeO2 solid solution shifted to red and the oxygen vacancy increased with lanthana content in Ce(1-x)La(x)O(2-x/2). The oxygen vacancy, generated by La3+ substituting for Ce4+, could supply more channels for oxygen migration through the lattice. The changes of lattice structure and the oxygen vacancy with La2O3 are correspondence with the results of oxygen storage capacity (OSC) measurement, which indicate that the changes of macro-performance are connected with the microstructure deformation of La2O3-CeO2. The kinetics of Ce0.9La0.2O1.9 nanomaterials with the highest OSC value was studied and the apparent activation energy (E(a)) of reduction and oxidation process was calculated to be 5.6 and 6.0 kJ/mol, respectively. The low E(a) value might be one of the reasons for Ce0.8La0.2O1.9 nanomaterials with the high OSC value.  相似文献   

14.
A detailed elaboration of the transformations of iron species, present in natural and Fe(NO(3))(3) loaded montmorillonite, during carbon deposition and carbon nanotube growth is described. According to transmission electron microscopy results, deposited carbon atoms form fibres in the case of pristine montmorillonite and multiwalled carbon nanotubes in the case of Fe(III) loaded montmorillonite. M?ssbauer and x-ray diffraction analysis results point to an extensive reduction of structural and intercalated Fe(III) cations to Fe(II) with the latter migrating from the interlayer space to the vacant octahedral sites of the mineral's lattice. Such migration of the non-structural iron catalyst prohibits extensive contamination of the final composite with various metal catalyst impurities. The crucial role of the active catalytic centres in the formation of carbon nanotubes is ascribed to a minor quantity of iron, found entrapped in the carbon nanostructures, which, at the end of the reaction, is identified as iron carbide. The interesting formation of a nanometric γ-iron precipitate is also detected, which is probably stabilized through strong interactions with the lattice of montmorillonite. Finally, it is demonstrated that iron-rich natural clay minerals can serve as direct catalysts for carbon nanotube growth.  相似文献   

15.
采用溶胶.凝胶法制备了负载型复合半导体光催化材料ZnFe2O4-TiO2/SiO2,并通过DTA-TG、XRD、XPS、Raman、TPR及UV-Vis DRS等实验技术对复合材料的晶体结构、表面组成及光响应性能进行了表征和评价.结果表明:ZnFe2O4晶相以高分散状态存在于光催化材料的表面;ZnFe2O4与TiO2复合可使部分Fe^3+进入体相TiO2的晶格中,促进其由锐钛矿向金红石的相转变,同时表面剩余的少量Zn计聚集形成ZnO物相;TiO2的相变由体相开始,随着ZnFe2O4含量的增加逐渐向表面扩展;SiO2的加入使活性组分更加分散,TiO2平均粒径〈10nm;ZnFe2O4的加入明显拓宽了TiO2的吸光域,并增强了对可见光的吸收.  相似文献   

16.
《Zeolites》1990,10(7):685-689
The state of iron in natural zeolites is an important feature for the practical applications of these materials. A Mössbauer study, complemented with other methods, of iron-containing zeolitic rocks from several countries (Mexico, Cuba, Czechoslovakia, and the USSR) was developed. It has been determined that iron is located as high spin Fe3+ in framework tetrahedral sites, in extraframework octahedral sites as free Fe(H2O)63+, and as high spin Fe2+ in octahedral coordination in extraframework sites or in another aluminosilicate associated with the zeolite. Iron is also located in magnetite contained in the zeolite rocks.  相似文献   

17.
Nonstoichiometric Fe-Ti spinel (Fe(3-x)Ti(x))(1-δ)O(4) has a large amount of cation vacancies on the surface, which may provide active sites for pollutant adsorption. Meanwhile, its magnetic property makes it separable from the complex multiphase system for recycling, and for safe disposal of the adsorbed toxin. Therefore, (Fe(3-x)Ti(x))(1-δ)O(4) may be a promising sorbent in environmental applications. Herein, (Fe(3-x)Ti(x))(1-δ)O(4) is used as a magnetically separable sorbent for elemental mercury capture from the flue gas of coal-fired power plants. (Fe(2)Ti)(0.8)O(4) shows a moderate capacity (about 1.0 mg g(-1) at 250 °C) for elemental mercury capture in the presence of 1000 ppmv of SO(2). Meanwhile, the sorbent can be readily separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed mercury.  相似文献   

18.
Mixed-valence manganites with the ABO3 perovskite structure display a variety of magnetic and structural transitions, dramatic changes of electrical conductivity and magnetoresistance effects. The physical properties vary with the relative concentration of Mn3+ and Mn4+ in the octahedral corner-sharing network, and the proportion of these two cations is usually changed by doping the trivalent large A cation (for example, La3+) with divalent cations. As the dopant and the original cation have, in general, different sizes, and as they are distributed randomly in the structure, such systems are characterized by local distortions that make it difficult to obtain direct information about their crystallographic and physical properties. On the other hand, the double oxides of formula AA'3Mn4O12 contain a perovskite-like network of oxygen octahedra centred on the Mn cations, coupled with an ordered arrangement of the A and A' cations, whose valences control the proportion of Mn3+ and Mn4+ in the structure. The compound investigated in this work, (NaMn3+(3))(Mn3+(2)Mn4+(2))O12, contains an equal number of Mn3+ and Mn4+ in the octahedral sites. We show that the absence of disorder enables the unambiguous determination of symmetry, the direct observation of full, or nearly full, charge ordering of Mn3+ and Mn4+ in distinct crystallographic sites, and a nearly perfect orbital ordering of the Mn3+ octahedra.  相似文献   

19.
Self-assembled ultrathin Ni(x)Fe(1-x)(OH)2 nanodiscs have been synthesized by using a wet-chemistry method. The uniformity and the assembly of Ni(x)Fe(1-x)(OH)2 nanostructures are sensitive to the iron ion concentration in the precursor. An optimum iron concentration of 10% results in the formation of uniform ultrathin Ni(x)Fe(1-x)(OH)2 nanodiscs with a typical side length of 50 nm and a thickness of 10 nm. They are also self-assembled by connecting their (001) facets with in-plane orientation and form a chain-like microstructure. Lattice relaxation is present within several atomic layers at the interfaces between two adjacent nanodiscs, which introduces about 6 degrees misalignment of these nanocrystals. Analytical electron microscopy analysis reveals that the iron additive atoms distribute uniformly in the nanodiscs and they are substitution atoms of Ni atoms. It has been found that the iron species is critical to the formation and assembly of the hexagonal nanodiscs.  相似文献   

20.
从理论和实验上分析了Fe^3+和Fe^2+对(BiA)YIG薄膜的生长感各向异性的贡献,掺Bi导致的生长磁感生各向异性,来源于Ei^3+改变了Fe^3+的零场劈裂,其大小取决于Bi^3+含量及在十二面体位的择优分布,高价离子和氧空位形成的Fe^2+在八面体位的择优分布,对生长感生磁各向异性也有贡献。  相似文献   

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