High-pressure synthesis and crystal structure analysis of NaMn2O4 with the calcium ferrite-type structure

Single crystals of a new sodium manganese oxide, NaMn₂O₄, were synthesized for the first time using a high-temperature and high-pressure technique. The NaMn₂O₄ single crystal is black, has a needle shape, and crystallizes in the orthorhombic calcium ferrite-type structure, space group Pnam with , , , , and Z=4. The structure was determined from a single-crystal X-ray study and refined to the conventional values R=0.041 and wR=0.034 for 1190 observed reflections. The framework structure is built up from edge-sharing chains of MnO₆ octahedra that condense to form one-dimensional tunnels in which the sodium atoms are located. The Mn-O bond distance and bond valence analyses revealed the manganese valence Mn³⁺/Mn⁴⁺ ordering in the two “double rutile” chains of NaMn₂O₄.     

Effect of LaFeO3 Decoration and Ozone Treatment on Thermal Stability of Au/Al2O3 for CO Oxidation

The 1.1%Au/LaFeO_x/Al₂O₃ catalysts were prepared by the iso-volume impregnation method and activated with H₂ or O₃. The catalytic performance for CO oxidation at room temperature was investigated by accelerated deactivation tests in 1.0% CO reactant stream at 550 °C. The introduction of La and Fe enhanced the thermal stability of Au/Al₂O₃ with a decrease in initial activity, probably due to the formation of LaFeO₃ perovskite on the Al₂O₃ surface. The 1.1%Au/2%LaFeO₃/Al₂O₃ catalyst activated by H₂ can transform 65% CO into CO₂ at room temperature after pretreatment in 1.0% CO reactant stream at 550 °C for 2 h, whereas 1.1%Au/Al₂O₃ activated by H₂ totally loses its activity. O₃ activation can always make 1.1%Au/LaFeO₃/Al₂O₃ more active than that of H₂ activation during the pretreatment process in 1.0% CO. After pretreatment for 10 h, 1.1%Au/2%LaFeO₃/Al₂O₃ activated by O₃ still shows 40% conversion of 1.0% CO at room temperature, whereas those activated by H₂ become inactive completely. The better thermal stability of the catalysts activated by O₃ may be due to that O₃ activation leads to the formation of partially oxidized state of Au in Au/FLA-O₃, which may reinforce the interaction between the metal and support.     

Evaluation of the catalytic effect of ZnO as a secondary phase in the Ni0.5Zn0.5Fe2O4 system and of the stirring mechanism on biodiesel production reaction

In search of efficient ways to produce biodiesel under environmentally friendly conditions, catalytic reactions have been explored with emphasis on replacing homogeneous by heterogeneous catalysis with the use of new catalyst types, such as the spinel ferrites, which are described as a viable option, since they are stable, highly active, inexpensive, reusable, and allow the easy recovery of the reaction medium through the application of magnetic fields. In this context, the present work proposes to contribute to the consolidation of the catalytic viability of the Ni_0.5Zn_0.5Fe₂O₄ system obtained by combustion reaction, because although previous studies indicate the catalytic effectiveness of this system in polyphasic form, the present work seeks as differential to evaluate the influence of the secondary phases and magnetization of the Ni-Zn system in the conversion to biodiesel, and for this purpose, it aims to evaluate the catalytic effect of ZnO formed as secondary phase and obtained concomitantly in the Ni-Zn ferrite synthesis, besides evaluating the effect of the stirring mechanism used in biodiesel production reaction by the ethyl transesterification of soybean oil. The synthesized Ni-Zn ferrites and ZnO sample were characterized by X-ray diffraction (XRD), nitrogen adsorption textural analysis (BET), particle size distribution, and then, tested in two reactor types, one with magnetic stirring, and another of mechanical stirring, to observe the magnetization effect of the material, and the characterization of the obtained biodiesels by gas chromatography (GC) and acidity index. The performed catalytic tests showed that the Ni-Zn ferrites promoted excellent ester conversions with values near and above 94%, thus confirming that although ZnO also promotes good ester conversion (83.9%), the catalytic effectiveness of the Ni-Zn ferrite is evident and independent of secondary phases. Moreover, the catalytic tests performed in the magnetic stirring reactor using the Ni-Zn ferrites as catalysts made it possible to realize that their magnetic properties may be interference in the catalytic effectiveness, being this, a more determining factor than the surface characteristics.     

Catalytic performance of NiFe2O4 and Ni0.3Zn0.7Fe2O4 magnetic nanoparticles during biodiesel production

In this study, catalytic performance of nanoferrites NiFe₂O₄ and Ni_0.3Zn_0.7Fe₂O₄ is reported. Nickel–ferrite and mixed nickel–zinc ferrite were successfully synthesized by combustion reaction using a conical reactor with production of 10 g per batch. Crystallinity and purity or quantitative analysis of the catalyst were checked by using X-ray diffraction and energy dispersive X-ray analysis. Surface chemistry was examined via Fourier transform infrared (FTIR) analysis; N₂ physisorption at 77 K was conducted to obtain textural properties of the catalyst; a thermogravimetric analysis, a scanning electron microscope and a transmission electron microscopy were used to check the thermal stability and morphology of the catalyst, respectively. The catalysts were used to convert soybean oil into biodiesel in a batch mode and the reaction mixture was analyzed using a pre-calibrated gas chromatograph (GC). The presence of a single-phase spinel structure in the synthesized nanoparticles was confirmed by the XRD results. The Ni_0.3Zn_0.7Fe₂O₄ had a lower surface area value of 71.5 m²g⁻¹ and higher saturation magnetization value of 31.50 emu/g than sample NiFe₂O₄ which had 87.6 m²g⁻¹ and 17.85 emu/g, respectively. Biodiesel yield of 94% was obtained with Ni_0.3Zn_0.7Fe₂O₄ and 49% was obtained with NiFe₂O₄. Better performance of Ni_0.3Zn_0.7Fe₂O₄ when compared to that of NiFe₂O₄ could be attributed to higher acidity of the former. Findings from this study suggest that the development of nickel-zinc ferrite nanoparticles as magnetic heterogeneous catalysts could provide an environmentally friendly platform for biodiesel production.     

沸腾回流法制备纳米NiZn铁氧体的研究

Nanometer NiZn ferrite powder with spinel structure was prepared by a new chemical method —— refluxing method. Refluxing time and pH value of coprecipitation were discussed based on the XRD analysis and pH value measurement. The optimum refluxing time and pH value of coprecititation were 6 hours and 9.5~11.0, respectively. Ni_0.5Zn_0.5Fe₂O₄ powder prepared by refluxing method was about 20 nm by TEM analysis. And VSM results revealed that the prepared Ni_0.5Zn_0.5Fe₂O₄ powder had typical soft magnetic characteristics.     

Nanocrystalline ferrites NixZn1−xFe2O4: Influence of cation distribution on acidic and gas sensing properties

This work is devoted to a detailed analysis of the interconnection between composition, cation distribution and acidic properties of the surface of nanocrystalline ferrites Ni_xZn_1−xFe₂O₄ obtained by aerosol pyrolysis. The detailed analysis of the Mössbauer spectra allows us to determine the distribution of cations between tetrahedral and octahedral positions in spinel structure. Depending on samples composition, the tetrahedral positions can be occupied by only Fe³⁺ cations (inverse spinel, x≥0.4) or by Fe³⁺ and Zn²⁺ cations (mixed spinel, x=0, 0.2). Increasing the nickel concentration in the ferrite leads to decrease in the number of strong acid centers on the surface. It was found that the decrease in the contribution of strong surface acid sites leads to an increase in sensory sensitivity of the ferrite towards ammonia. For ethanol detection an inverse relationship between sensor signal and surface acidity was observed.     

Oriented SrFe12O19 thin films prepared by chemical solution deposition

Thin films of SrFe₁₂O₁₉ (SrM) were prepared from a solution of iron and strontium alkoxides through the chemical solution deposition method on both amorphous (glassy SiO₂), and single crystal substrates (Si(100), Si(111), Ag(111), Al₂O₃(001), MgO(111), MgAl₂O₄(111), SrTiO₃(111)) substrates. The process of crystallization was investigated by means of powder diffraction, atomic force microscopy and scanning electron microscopy. Magnetization measurements, ferromagnetic and nuclear magnetic resonance were used for evaluation of anisotropy in the films. Whilst amorphous substrates enabled growth of randomly oriented SrM phase, use of single crystal substrates resulted in samples with different degree of oriented growth. The most pronounced oriented growth was observed on SrTiO₃(111). A detailed inspection revealed that growth of SrM phase starts through the breakup of initially continuous film into isolated grains with expressive shape anisotropy and hexagonal habit. A continuous film with epitaxial relations to the substrate was produced by repeating recoating and annealing.     

红外导数光谱鉴定铁系复合氧化物中γ-Fe2O3

It is well known that γ-Fe_2O_3 is a very active and selective catalyst for okidative dehydrogenation ofbutene to butadiene. It is hard, however, to distingulsh between ferrite spinels and therefore to identify its existence in ferrite-ferric oxide catalysts using XRD. On the IR spectra γ-Fe_2O_3 has characteristic bands in the range of 600~800 cm~(-1), which do not exist for α-Fe_2O_3, Fe3O4, ZnFe_2O_4 and MgFe_2O_4. But these bands are too weak to deterAnne for the small amount of γ-Fe_2O_3, e g. less than 30% (mass fraction), in catalysts.
Usually using second derivative IR spectra can increase the analytical sensitivity substantially. The mechanical mixtures of γ-Fe_2O_3 and MgFe_2O_4 in different ratio were prepared and their second derivative IR spectra were taken. It was found that the bands 730 and 695 cm~(-1) were characteristic of γ-Fe_2O_3 and their intensities increased with the content of γ-Fe_2O_3 in the mixtures. A staight line with R=0.994 can describe the relation between γ-Fe_2O_3 content and the peak area of band 695 cm~(-1). The lowest detectable content of γ-Fe_2O_3 is about 1% (mass fraction). The existence of γ-Fe_2O_3 in the used B-02 comercial catalyst was identified by this method.     

氧化镍-铁酸锌复合薄膜/锡掺杂玻璃光波导传感元件的制备及其对硫化氢气体的气敏性

用溶胶-凝胶法制成了NiO掺杂的ZnFe2O4溶胶,并用浸渍提拉法将其固定在锡掺杂玻璃光波导表面,研制了NiO-ZnFe2O4复合薄膜/锡掺杂玻璃光波导气敏元件,并对无机有毒气体进行了检测。 实验结果表明,在室温下,该传感元件对H2S气体具有一定的选择性响应,而对相同浓度的其它无机气体的响应相对较小,能够检测到1.0×10-9（体积比）的H2S气体,其响应和恢复时间分别是6和8 s。 该元件具有灵敏度高、响应-恢复快、可逆性和重复性好、容易制备,在室温下便于操作等特点。     

镍锌铁氧体/膨胀石墨/聚苯胺复合物的电磁损耗性能

用化学共沉淀法和原位乳液聚合法分别制备了镍锌铁氧体(NixZn1-xFe2O4)、Ni0.7Zn0.3Fe2O4/膨胀石墨(NZF/EG)二元复合物及其聚苯胺(PANI)包覆的三元复合物(NZF/EG/PANI)。用现代测试技术表征了样品的组成、结构、形貌和电磁性能。结果表明,NZF粒子较好地嵌入到EG的层间,PANI对NZF/EG的包覆效果良好;三元复合物的磁性能随磁性组分含量的减小而减弱,而电导率与EG和PANI的导电性及其相对含量相关联;复合物的电磁损耗性能优良,其中三元复合物优于二元复合物。含PANI70wt%的NZF/EG/PANI三元复合物,制样厚度分别为1.5、2.0和2.5 mm时,其反射损耗峰值(有效带宽)分别为-19.99 d B(5.82GHz),-20.33 d B(4.08 GHz)和-25.28 d B(3.67 GHz),具有优良的电磁波吸收效果。