Comparing the Atomic Structures of Binary MO2-SiO2 (M = Ti, Zr or Hf) Xerogels

The incorporation of transition-metal oxides into silica can give materials with useful optical, electronic or catalytic properties. For example, ZrO₂-SiO₂ and HfO₂-SiO₂ materials are of interest due to their high dielectric constants. Here we present a comparison of extended X-ray absorption fine structure and small-angle X-ray scattering results for acid-catalysed binary (MO₂) _x (SiO₂)_{1 – x} (M = Ti, Zr or Hf) xerogels, with x up to 0.4 and heat treatments up to 750°C. Detailed observations for TiO₂-SiO₂ and ZrO₂-SiO₂ xerogels provide a basis for interpretation of new results for HfO₂-SiO₂ xerogels. At low concentrations metal atoms are homogeneously incorporated into the silica network. Ti adopts coordinations of 4 or 6, and Zr and Hf both adopt higher coordination of 6 or 7 (the larger coordinations being due to ambient moisture). At higher concentrations, phase separation of metal oxide occurs. Such regions become clearly separated from the silica network for TiO₂, but remain very finely mixed with silica network for ZrO₂ and HfO₂.     

Preparation of ZnO Nanoparticles: Structural Study of the Molecular Precursor

The structure of zinc acetate derived precursor currently used in the sol-gel synthesis of ZnO nanoparticles is described. The reaction products obtained before and after reflux of ethanolic zinc acetate solution have been studied by UV-Vis, photoluminescence, FTIR and EXAFS at the Zn K edge. EXAFS results evidence for both precursor solutions a change from the octahedral coordination sphere of oxygen atoms characteristic of the solid zinc acetate dihydrate compound into a four-fold environment. The EXAFS spectra of precursor solutions can be satisfactorily reproduced using the molecular structure reported for Zn₄O(Ac)₆ (Ac = COOCH₃). UV-Vis and FTIR measurements are also in agreement with the formation of this oligomeric precursor. The structural modification is more pronounced after reflux at 80°C, because the increase of the Zn₄O(Ac)₆ amount and the formation of nearly 3.0 nm sized ZnO nanoparticle.     

The synthesis and characterisation of ferromagnetic CaMn2O4 nanowires.

The synthesis of marokite CaMn(2)O(4) nanowires using a hydrothermal method is reported. Transmission electron microscopy and electron diffraction measurements show that the nanowires are polycrystalline in nature with diameters between 10 and 20 nm and lengths ranging from approximately 100 to 500 nm. Most interestingly, in contrast with the bulk material, magnetization measurements show that these nanowires exhibit ferromagnetic ordering with a Curie temperature (T(C)) of approximately 40 K.     

EXAFS Spectroscopy of the Alkoxide Precursor Zr(O n Bu)4 and its Modification in Solution

Summary. The molecular structure of the transition metal alkoxide Zr(OⁿBu)₄ in toluene and its modification by addition of i-propanol, tetrahydrofurane, and the coordinating ligand pentane-1,3-dione (Hacac) were investigated by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy. Zr(OⁿBu)₄ dissolved in toluene forms dimers. It was proved that cluster size is a function of the number of added equivalents ligand. In contrast, the addition of i-propanol or tetrahydrofurane caused no structural changes observable by EXAFS spectroscopy. A detailed discussion of the structural models is given in terms of possible alternatives and errors within the EXAFS analysis.     

Investigation of the Crystallisation Behaviour of Lead Titanate (PT), Lead Zirconate (PZ) and Lead Zirconate Titanate (PZT) by EXAFS-Spectroscopy and X-Ray Diffraction

Two solid solutions of lead zirconium titanates PbZr _x Ti_{1 – x} O₃ (x = 0.1 and 0.35) as well as the reference compounds lead titanate and lead zirconate were prepared from zirconium and titanium n-propoxide, dissolved in 2-methoxyethanol, by sol-gel process. The amorphous products after pyrolysis of the dried gels and the crystalline phases were studied by EXAFS spectroscopy to monitor the structural changes from the amorphous oxide mixture to the crystalline ceramics after calcination. Additionally, the crystalline phases were identified by X-ray diffraction (XRD).It follows from the analysis of the EXAFS data that the local order of the amorphous phases seems to be completely different from that of the crystalline phase. There is no indication of a preformation of the local order of the perovskite structure. The analysis of our EXAFS spectra can be interpreted very consistently with the assumption that in the amorphous samples a segregation exists on molecular level and the low crystallisation temperatures are a consequence of very short diffusion paths.     

Rapid monitoring of the nature and interconversion of supported catalyst phases and of their influence upon performance: CO oxidation to CO2 by gamma-Al2O3 supported Rh catalysts

Spatially and temporally resolved energy-dispersive EXAFS (EDE) has been utilised in situ to study supported Rh nanoparticles during CO oxidation by O2 under plug-flow conditions. Three distinct phases of Rh supported upon Al2O3 were identified by using EDE at the Rh K-edge during CO oxidation. Their presence and interconversion are related to the efficiency of the catalysts in oxidising CO to CO2. A metallic phase is only found at higher temperatures (>450 K) and CO fractions (CO/O2 > 1); an oxidic phase resembling Rh2O3 dominates the active catalyst under oxygen-rich conditions. Below about 573 K, and in CO-rich environments, high proportions of isolated Rh(I)(CO)2 species are found to co-exist with metallic Rh nanoparticles. Alongside these discrete situations a large proportion of the active phase space comprises small Rh cores surrounded by layers of active oxide. Confinement of Rh to nanoscale domains induces structural lability that influences catalytic behaviour. For CO oxidation over Rh/Al2O3 there are two redox phase equilibria alongside the chemistry of CO and O adsorbed upon extended Rh surfaces.     

Speciation of Rare‐Earth Metal Complexes in Ionic Liquids: A Multiple‐Technique Approach

The dissolution process of metal complexes in ionic liquids was investigated by a multiple‐technique approach to reveal the solvate species of the metal in solution. The task‐specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf₂N]) is able to dissolve stoichiometric amounts of the oxides of the rare‐earth elements. The crystal structures of the compounds [Eu₂(bet)₈(H₂O)₄][Tf₂N]₆, [Eu₂(bet)₈(H₂O)₂][Tf₂N]₆?2H₂O, and [Y₂(bet)₆(H₂O)₄][Tf₂N]₆ were found to consist of dimers. These rare‐earth complexes are well soluble in the ionic liquids [Hbet][Tf₂N] and [C₄mim][Tf₂N] (C₄mim=1‐butyl‐3‐methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, ¹H, ¹³C, and ⁸⁹Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X‐ray absorption fine structure) and HEXS (high‐energy X‐ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.     

硼和铟掺杂对Fe81Ga19快淬薄带的微结构、磁致伸缩性能及磁性的影响

通过甩带快淬法制备三元合金（Fe_0.81Ga_0.19）_100-xB_x （Fe-Ga-B）和（Fe_0.81Ga_0.19）_100-xIn_x （Fe-Ga-In）薄带样品,并对Fe-Ga-B合金样品进行热处理。通过高分辨X射线衍射（HRXRD）和扩展X射线吸收精细结构谱（EXAFS）技术表征薄带的微观结构,利用振动样品磁强计和标准电阻应变仪测量了样品的磁性及饱和磁致伸缩系数。研究表明,有序的L1₂相降低了（Fe_0.81Ga_0.19）₉₈B₂样品的磁致伸缩系数。B原子添加形成的Fe₂B相和modified-DO₃相有利于提高Fe-Ga合金的磁致伸缩系数。但Fe₂B相的饱和磁化强度小于A₂相,饱和磁场却远大于A₂相,因此随着B含量的增加,Fe-Ga-B薄带的饱和磁化强度逐渐减小,矫顽力逐渐增加。合金中形成的非磁性富In相使得In掺杂Fe-Ga-In合金的磁致伸缩系数和饱和磁化强度均减小。非磁性富In相使晶格产生畸变,减弱了磁弹性效应,并且抑制了磁畴的运动,从而明显地减小了Fe-Ga带材样品的磁致伸缩系数以及饱和磁化强度,提高了Fe-Ga合金的矫顽力。