Synthesis of LiFePO4 with fine particle by co-precipitation method

LiFePO₄ is a potential candidate for the cathode material of the lithium secondary batteries. A co-precipitation method was adopted to prepare LiFePO₄ because it is simple and cheap. Nitrogen gas was needed to prevent oxidation of Fe²⁺ in the aqueous solution. The co-precipitated precursor shows the high reactivity with the reductive gas, and the single phase of LiFePO₄ is successfully synthesized with the aid of carbon under less reductive conditions. LiFePO₄ fine powder prepared by co-precipitation method shows high rate capability, impressive specific capacity and cycle property.     

The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites

V-silicalite catalysts (VS-1 and VS-2) prepared by hydrothermal synthesis have been studied by ESR, XAFS (XANES and EXAFS) and photoluminescence spectroscopy. The in situ characterization of these V-silicalites shows that vanadium is present within the zeolitic framework as a highly dispersed tetrahedrally coordinated V-oxides, VO₄ unit, having a short V=O bond length. Photoluminescence spectroscopy in static and dynamic mode, as well as XAFS studies allow to detect in the V-silicalites different V species than that present in V-HMS or V/SiO₂, in terms of V=O bond length, vibrational energy, bond angle and lifetime of the excited triplet state. It is suggested that the combined contribution of the neighboring Si---OH group attached to the VO₄ unit and the zeolitic rigid framework structure of V-silicalites cause a more significant and pronounced effect on the chemical properties of the VO₄ unit than the flexible structure of V-HMS or V/SiO₂. Moreover, the dynamic quenching of the phosphorescence by the addition of reactant molecules such as NO or propane indicates that the V species in the excited triplet state can be expected to be the active sites for the photocatalytic reactions.     

Structural investigation of thin films of Ti1−xAlxN ternary nitrides using Ti K-edge X-ray absorption fine structure

Thin films of Ti_1−xAl_xN nitrides were prepared over a large range of composition (0 ≤ x < 1) on Si substrates using nitrogen reactive magnetron sputtering from composite metallic targets. Ti K-edge X-ray Absorption Spectroscopy experiments were carried for a better understanding of the local structure. The evolution of the intensity of Ti K-edge pre-edge peak gives evidence of the incorporation of Ti in hexagonal lattice of AlN for Al-rich films and in cubic lattice of TiN for Ti-rich films. An attempt to determine their atomic structure by combining X-ray diffraction and Ti K-edge Extended X-ray Absorption Fine Structure is presented. The evolution of the nearest neighbour and next-nearest neighbour distances depending on the composition is presented and discussed together the cubic and hexagonal lattice parameters. A possible contribution of amorphous nitrides is suggested.     

Local structural characterization of Zn:Cd:Se ternary semiconductors

We have studied the local atomic structure around Zn and Cd, in CdSe, ZnSe, and ordered and disordered Zn_0.5Cd_0.5Se thin films, grown by molecular beam epitaxy (MBE) and atomic layer epitaxy (ALE) using X-ray absorption spectroscopy (XAS). Zn K-shell X-ray absorption fine structure (XAFS) shows that the Zn–Se pair nearest neighbor distance is the same in both ordered and disordered ternary samples. This result shows that the ordered (or disordered growth) does not have a significant effect in the nearest neighbor Zn environment. However, results from K-shell Cd XAFS show that the Cd–Se pair nearest neighbor distance in the Zn_0.5Cd_0.5Se ordered film exhibits a contraction compared to the same pair distance in the disordered Zn_0.5Cd_0.5Se sample and the binary CdSe compound. This suggests that the shortest Zn–Se nearest neighbor distance regulates the Cd–Se nearest neighbor distance in the ternary compounds, when these are grown in an ordered, layer by layer, fashion.     

机械合金化Cu-Sn二元形状记忆非晶态合金的XAFS研究

利用X射线吸收精细结构(XAFS)方法研究了机械合金化(Mechanical alloying，MA)方法制备的Cu-Sn二元金属合金在球磨过程中的结构变化。研究结果定量地表明，随着球磨时间的增加，Cu-Cu的键长逐渐变大，Cu第一近邻Cu-Cu配位数减小；Cu-Sn配位数逐渐增大，Cu与Sn的合金化程度和均匀性也随之增加。球磨4h后，Cu-Cu的配位数由Cu粉的12降低为7．4，键长由2．55A增加到2．63A；球磨12h后，Cu-Cu的配位数降低到6．4，Cu-Sn的配位数由O变到5．1，键长约为2．8A左右；球磨72h的结果与球磨12h的结果相近，说明Cu与Sn的互扩散过程基本达到平衡，形成组成近似于Cu6Sn5的非晶合金。     

How Different Characterization Techniques Elucidate the Nature of the Gold Species in a Polycrystalline Au/TiO2 Catalyst

TiO₂‐supported gold species were prepared via the deposition‐precipitation route, with conservation of the initial speciation by freeze‐drying. The structural and electronic properties of the Au species were investigated by X‐ray absorption spectroscopy, electron microscopy, and IR spectroscopy of adsorbed CO in four states. Exclusively Au^III was deposited on the TiO₂ surface in patches ranging from isolated Au ions to three‐dimensional clusters. This paper illustrates in detail the unique contributions of all characterization techniques to this structural model.     

Substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of perovskite-structured Ba(In0.5Ta0.5−xBix)O3 semiconductors

We have investigated the substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of barium indium tantalate. X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that, under oxygen atmosphere of 1 atm, pentavalent Bi ions are successfully stabilized in the octahedral site of the perovskite tantalate lattice. According to diffuse reflectance UV-vis spectroscopic analysis, the Bi substitution gives rise to the significant narrowing of band gap of barium indium tantalate even at a low Bi content of ∼5%, underscoring a high efficiency of Bi substitution in the band gap engineering. Such an effective narrowing of the band gap upon the Bi substitution would be attributable to the lowering of conduction band position due to the high electronegativity of Bi^V substituent. As a result of band gap engineering, the Ba(In_0.5Ta_0.5−xBi_x)O₃ compounds with x ≥ 0.03 can generate photocurrents under visible light irradiation (λ > 420 nm). Based on the present experimental findings, it becomes clear that the substitution of highly electronegative p-block element like Bi^V ion can provide a very powerful tool for tailoring the electronic structure and physicochemical properties of wide band gap semiconductors.     

Ce K-edge EXAFS study of nanocrystalline CeO2

Nanocrystalline CeO₂ samples were prepared via precipitation from aqueous cerium(IV) sulfate solution under a controlled pH. After being subjected to calcination at various temperatures to yield different particle sizes, the local structure around Ce atom was investigated by using EXAFS spectroscopy at Ce K-edge. The first shell CeO distance was found to be slightly shorter with small CeO₂ particles, indicating a contraction of the lattice. There exists a significant growth in coordination number of the second cell CeCe when the particle size became larger. In terms of Debye-Waller factor (σ²), the first three coordination shells showed a consistent trend, i.e. the degree of disorder increases with reduced particle size. Moreover, σ² of the second shell was found to be smaller than that of the first shell for all samples.     

Study of local environment of Ag in Ag/CeO2 catalyst by EXAFS

The combustion synthesized Ag/CeO₂ catalysts have been characterized by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy at the Ag K-edge. It has been found that Ag⁺ like species is present in 1% Ag/CeO₂ catalyst, whereas mostly Ag metal clusters are found in 3% Ag/CeO₂. The analysis of EXAFS spectra indicates that about one oxygen atom is coordinated to Ag central atom at a distance of 2.19 Å in 1% Ag/CeO₂ catalyst along with eight coordinated AgAg bond at 2.86 Å. The AgO bond is absent in 3% Ag/CeO₂.