铁微量掺杂对二钛酸钡陶瓷介电性能的影响

采用常规固相反应法,以碳酸钡、二氧化钛和三氧化二铁为原料,制备微量铁掺杂的二钛酸钡陶瓷,研究了铁掺杂含量对二钛酸钡陶瓷的相纯度、相对密度和介电性能的影响.采用X射线粉末衍射仪检测二钛酸钡陶瓷的相成分,利用精密阻抗分析仪测量其介电性能.结果表明,微量铁元素进入了二钛酸钡晶格,能够获得单相二钛酸钡陶瓷的最大铁掺杂量在0.5%～1%之间.随着铁含量的增加,铁电相变居里温度快速减小,从未掺杂时的415 ℃降至铁含量为0.02%时的376 ℃和铁含量为0.5%时的324 ℃.同时介电常数逐渐减小,介电峰不断发生宽化,但并没有导致弛豫性铁电体的出现.微量铁元素的掺杂在实验测量误差范围内对陶瓷的密度影响不大.     

Role of iron in the ferromagnetic-antiferromagnetic boundary of La0.5Ca0.5Mn1-xFexO3+δ (0≤x≤0.5) manganites

Samples of La_0.5Ca_0.5Mn_1−xFe_xO_3+δ (0≤x≤0.5) were synthesized using a solid-state reaction method involving a milling process and thermal treatment up to 1200 °C in an air atmosphere. Samples were characterized structurally with X-ray diffraction analysis and Rietveld refinement with morphology characterization using scanning electron microscopy. Magnetic properties were investigated using a physical property measurement system to obtain zero field cooling and the associated curves to plot hysteresis loops. Our results revealed the interplay between the structural and magnetic properties as Fe ions attached to the crystalline structure. A mechanism based on the substitution of Mn³⁺ and Mn⁴⁺ by low-spin Fe³⁺ and Fe⁴⁺ ions, respectively, was hypothesized to interpret the experimental data. More specifically, the temperature at which the transition from ferromagnetic to paramagnetic occurred increased with increasing Fe content as a result of a greater density of oxygen-mediated ferromagnetic bonds. Conversely, the magnetization weakened because the t_2g electrons were distributed in the respective d orbitals by adopting a low-spin configuration. Such a configuration is preferred as a result of the unit cell distortion in the milling process where the greater ionic radius of the Fe⁴⁺ ions leads to an elongated c-axis tetragonal symmetry and a greater unit cell volume. Finally, low-temperature magnetic behavior revealed the occurrence of a reentrant spin-glass type state within the ferromagnetic matrix favored by a milling-driven structural disorder and the existence of competitive superexchange interactions.     

反溶剂沉淀法合成Fe3+掺杂ZnO纳米结构及其可见光催化性能

以氯化胆碱-草酸低共熔溶剂(ChCl-OA DES)为溶剂，ZnO和Fe₂O₃为原料，通过简单的反溶剂沉淀法制备出不同掺杂浓度的Fe³⁺掺杂ZnO(Fe-ZnO)纳米结构。采用SEM、XRD、拉曼光谱、XPS等手段对所制Fe-ZnO结构与形貌进行了表征。结果表明，Fe-ZnO是由直径为20～30 nm纳米晶组装而成的微米棒。不同掺杂浓度的Fe-ZnO纳米晶均为六方铅锌矿结构，Fe³⁺很好地进入ZnO晶格。同时考察了所制Fe-ZnO的光吸收特性和光催化活性，发现Fe³⁺掺杂使其吸收峰红移至可见光范围，有效增强了可见光区域的催化活性。当Fe掺杂量为1.0%(atom)时，样品的光催化活性最好，比ZnO增大了约102倍。这说明Fe³⁺掺杂可改善ZnO对可见光光子的捕获能力。     

Fe-doped CoP nanotube heterostructure enhanced the catalytic activity of Pt nanoparticles towards methanol oxidation reaction

Developing the efficient and stable anode catalysts of direct methanol fuel cell has been a pivotal requirement for its extensive commercial application. Herein, we design the Fe-doped CoP nanotube heterostructure as the co-catalyst of Pt-based catalyst via combining a facile hydrothermal with phosphorization process, subsequently, the traditional NaBH₄ reduction method is utilized to deposit Pt nanoparticles. As anticipated, Fe species have been successfully doped into CoP to generate the Fe-doped CoP nanotube heterostructure, and the involved characterizations identify that Pt–C/Fe₂–CoP catalyst exhibits admirable mass activity (1237 mA·mg⁻¹_Pt) towards methanol oxidation reaction, which is approximately 2.04 and 3.66 times as high as the Pt–C/CoP (607 mA·mg⁻¹_Pt) and Pt–C–H (338 mA·mg⁻¹_Pt). After stability test, the decline ratio of mass activity for Pt–C/Fe₂–CoP (83.43%) is markedly preferable to Pt–C/CoP (94.92%) and Pt–C–H (98.67%) catalysts. The enhanced catalytic activity and durability can be imputed to the formation of uniform Pt nanoparticles and co-catalysis effect of Fe-doped CoP nanotube heterostructure since the introduction of hetero-metal cations is able to effectively accelerate the charge transfer rate and adjust the electronic structure of material. Therefore, the fabrication of nanotube heterostructure and introduction of hetero-metal may provide a new direction to the development of other high-efficiency electrocatalysts.     

(Ni0.75Fe0.25-xMgO)/YSZ anode for direct methane solid-oxide fuel cells

(Ni_0.75Fe_0.25-xMgO)/YSZ samples—with a varying weight percentage x (0, 5%, 10%) of MgO with respect to Ni_0.75Fe_0.25—were prepared and studied as anodes for intermediate temperature solid oxide fuel cells (SOFCs) operated on humidified methane (3% H₂O). Among the cells with different anode compositions, it was found that the cell with the (Ni_0.75Fe_0.25-5%MgO)/YSZ anode showed the highest power density, giving 648 mW cm⁻² at 800 °C. The cells with MgO-doped anodes were able to operate stably for 20 h under a current density of 0.53 A cm⁻² at 700 °C without observed degradation, while the cells without MgO degraded rapidly. The mechanisms responsible for the superior performance and duration of the (Ni_0.75Fe_0.25-5%MgO)/YSZ anode were analyzed.     

Fe掺杂对纳米复合Ag-SnO2电接触合金电弧演化行为的影响

应用高速数字摄像机和扫描电镜对纳米复合Ag-SnO2，Fe掺杂的纳米复合Ag-SnO2及商用Ag—SnO2-In2O3电接触合金的电弧演化过程和阴极斑点进行了比较研究。结果显示：空气中电弧的演化过程可以分为起弧、稳定燃烧和衰减3个阶段。Fe掺杂后，纳米复合电接触合金电弧演化过程的形弧时间是商用合金的2倍；对触点表面烧蚀起主要作用的稳定燃烧时间短；电弧弧根对应的阴极斑点数量多、跳动迅速、运动区域大；电弧弧根在阴极表面停留的时间短，热流输入少，使其燃弧后阴极斑点分散，烧蚀轻微，具有较好的耐电弧侵蚀性能。     

Preparation, characterization and visible-light-driven photocatalytic activity of Fe-doped titania nanorods and first-principles study for electronic structures

Fe-doped TiO₂ (Fe-TiO₂) nanorods were prepared by an impregnating-calcination method using the hydrothermally prepared titanate nanotubes as precursors and Fe(NO₃)₃ as dopant. The as-prepared samples were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, N₂ adsorption–desorption isotherms and UV–vis spectroscopy. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air under visible-light irradiation. The results show that Fe-doping greatly enhance the visible-light photocatalytic activity of mesoporous TiO₂ nanorods, and when the atomic ratio of Fe/Ti (R_Fe) is in the range of 0.1–1.0%, the photocatalytic activity of the samples is higher than that of Degussa P25 and pure TiO₂ nanorods. At R_Fe = 0.5%, the photocatalytic activity of Fe-TiO₂ nanorods exceeds that of Degussa P25 by a factor of more than two times. This is ascribed to the fact that the one-dimensional nanostructure can enhance the transfer and transport of charge carrier, the Fe-doping induces the shift of the absorption edge into the visible-light range with the narrowing of the band gap and reduces the recombination of photo-generated electrons and holes. Furthermore, the first-principle density functional theory (DFT) calculation further confirms the red shift of absorption edges and the narrowing of band gap of Fe-TiO₂ nanorods.     

Enhanced microwave absorption properties of Fe-doped SiOC ceramics by the magnetic-dielectric loss properties

The combination of multiple loss characteristics is an effective approach to achieve broadband microwave wave absorption performance. The Fe-doped SiOC ceramics were synthesized by polymer derived ceramics (PDCs) method at 1500 °C, and their dielectric and magnetic properties were investigated at 2–18 GHz. The results showed that adding Fe content effectively controlled the composition and content of multiphase products (such as Fe₃Si, SiC, SiO₂ and turbostratic carbon). Meanwhile, the Fe promoted the change of the grain size. The Fe₃Si enhanced the magnetic loss, and the SiC and turbostratic carbon generated by PDCs process significantly increased the polarization and conductance loss. Besides, the magnetic particles Fe₃Si and dielectric particles SiO₂ improved the impedance matching, which was beneficial to EM wave absorption properties. Impressively, the Fe-doped SiOC ceramics (with Fe addition of 3 wt %) presented the minimum reflection coefficient (RC_min) of ?20.5 dB at 10.8 GHz with 2.8 mm. The effective absorption bandwidth (EAB, RC < ?10 dB) covered a wide frequency range from 5 GHz to 18 GHz (covered the C, X and Ku-band) when the absorbent thickness increased from 2 mm to 5 mm. Therefore, this research opens up another strategy for exploring novel SiOC ceramics to design the good EM wave-absorbing materials with broad absorption bandwidth and thin thickness.     

铁掺杂PbO2/Ti电极电催化氧化苯酚的实验研究

以苯酚为目标化合物,研究了新型铁掺杂PbO2/Ti阳极电催化氧化有机污染物的特性,结果表明,该电极对苯酚的降解显示了良好的电催化活性,有较好的环保应用前景。同时,初步探讨了反应的动力学和氧化机理。     

Influence of gamma irradiation on the refractive index of Fe-doped barium titanate thin films

Polycrystalline Fe-doped barium titanate (Fe-doped BaTiO₃) thin films were grown by thermal decomposition of the precursors deposited from a sol-gel system onto quartz substrates. The changes in the transmittance spectra induced by gamma irradiation on the Fe-doped BaTiO₃ thin films were quantified. The values for the optical energy band gap were in the range of 3.42-3.95 eV depending on the annealing time. The refractive index of the film, as measured in the 350-750 nm wavelength range was in the 2.17-1.88 range for the as prepared film, and this increased to 2.34-1.95 after gamma irradiation at 15 kGy. The extinction coefficient of the film was in the order of 10⁻² and increased after gamma irradiation. We obtained tuneable complex refractive index of the films by exposure to various gamma rays doses.