Local structure and optical absorption characteristic investigation on Fe doped TiO_2 nanoparticles

The local structures and optical absorption characteristics of Fe doped Ti O2 nanoparticles synthesized by the sol-gel method were characterized by X-ray diffraction(XRD), X-ray absorption fine structure spectroscopy(XAFS) and ultraviolet-visible absorption spectroscopy(UV-Vis). XRD patterns show that all Fe-doped Ti O2 samples have the characteristic anatase structure. Accurate Fe and Ti K-edge EXAFS analysis further reveal that all Fe atoms replace Ti atoms in the anatase lattice. The analysis of UV-Vis data shows a red shift to the visible range. According to the above results, we claim that substitutional Fe atoms lead to the formation of structural defects and new intermediate energy levels appear, narrowing the band gap and extending the optical absorption edge towards the visible region.     

Radial-distribution function by EXAFS: Asymmetry in metallic glasses

Summary The authors discuss the information on the radial-distribution function (RDF) obtainable from EXAFS as compared with X-ray diffraction. The cases of Gaussian and non-Gaussian RDFs are illustrated showing how the Fourier transform (FT) of the experimental spectrum is connected with the RDF parameters in the two cases. The evidence of an asymmetric RDF in a metal glass, Fe₈₀B₂₀, is presented and discussed in detail. Paper presented at the Workshop on ?EXAFS Data Analysis in Disordered Systems?, held in Parma, October 5–7, 1981.     

Microstructural properties and local atomic structures of cobalt oxide nanoparticles synthesised by mechanical ball-milling process

In this study, facile preparation of pure and nano-sized cobalt oxides particles was achieved using low-cost mechanical ball-milling synthesis route. Microstructural and morphological properties of synthesised products were characterised by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. XRD results indicated that the fabricated samples composed of cubic pure phase CoO and Co₃O₄ nanocrystalline particles with an average crystallite size of 37.2 and 31.8 nm, respectively. TEM images showed that the resulting samples consisted of agglomerates of particles with average diameter of about 37.6 nm for CoO and 31.9 nm for Co₃O₄. Phase purity of the prepared samples was further investigated due to their promising technological applications. Local atomic structure properties of the prepared nanoparticles were probed using synchrotron radiation-based X-ray absorption spectroscopy (XAS) including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). EXAFS data analysis further confirmed the formation of single-phase CoO and Co₃O₄ nanoparticles. In addition, structural properties of cobalt oxide nanoparticles were investigated by performing density functional theory calculations at B3LYP/TZVP level and Born–Oppenheimer molecular dynamics. Theoretical calculations for both prepared samples were found to be consistent with the experimental results derived from EXAFS analysis. Obtained results herein reveals that highly crystalline and pure phase CoO and Co₃O₄ nanoparticles can be synthesised using simple, inexpensive and eco-friendly ball-milling method for renewable energy applications involving fuel cells and water splitting devices.     

Local surrounding of Mn in LaMn1−xCoxO3 compounds by means of EXAFS on Mn–K

A systematic study of LaMn_1?xCo_xO₃ perovskite series by means of X-ray absorption spectroscopy in the extended X-ray absorption fine structure (EXAFS) range of the K-absorption edge of Mn is reported. The Mn–K edge absorption measurements in the EXAFS region were performed to study the local surrounding of Mn ions. Polycrystalline powder samples of LaMn_1?xCo_xO₃ (x=0, 0.02; 0.2; 0.4; 0.5; 0.6; 0.8) prepared by solid-state reaction were used. The EXAFS spectra were analyzed with the FEFF8 computer program. The Mn–O distances of Mn to the nearest oxygen surroundings were evaluated for the samples in the series and compared with the Co–O distances obtained by EXAFS in V. Procházka et al., JMMM 310 (2007) 197 and with results of X-ray powder diffraction in C. Autret, J. Phys. Condens. Matter 17 (2005) 1601.     

Structural and magnetic properties of FeB microfibers

Structural and magnetic properties of FeB microfibers, obtained by electroless deposition on cellulose fibers, were investigated. X-ray diffraction (XRD) showed the presence of an amorphous phase. Extended X-ray absorption fine structure spectroscopy (EXAFS) studies confirmed an amorphous-like structure with the nearest coordination numbers around Fe atom to be 8.7 for Fe and 3.5 for B. The magnetic moment of 2.12 Bohr magnetons/Fe atom is consistent with composition obtained from EXAFS measurements. PACS 61.43.Dq; 61.10.Ht; 75.70.-i; 61.10.Eq; 81.15.Pq     

非晶和纳米ZrO2·Y2O3(15%)的X射线衍射与扩展X射线吸收精细结构研究

利用粉末X射线衍射和扩展X射线吸收精细结构(EXAFS)技术对用化学共沉淀法制备的非晶和纳米ZrO₂·15%Y₂O₃体系进行了研究.粉末X射线衍射结果表明,300℃温度处理的样品呈非晶态,500℃时样品已经晶化,形成单一立方相的纳米结构.EXAFS分析显示,在从非晶态向纳米结构晶化的过程中,最近邻的ZrO配位层的配位数和键长没有发生明显的改变,说明300℃时已经形成和900℃相同的最近邻局域结构.而对于ZrZr(Y)配位层,随着晶粒尺寸的减 关键词： EXAFS 晶化 配位数 键长     

The characterization of EuO nanocrystals using synchrotron light

We have studied the physical structure, optical property, electronic band structure and atomic structure of europium oxide (EuO) nanocrystals. The physical structures of nanocrystals are confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The optical property and electronic band structure are studied by X-ray absorption near-edge structure (XANES) measurement. We have also investigated the L₃-edge energy of europium(II) ion by extended X-ray absorption fine structure (EXAFS) measurement, which clarified the atomic structure of europium oxide nanocrystals.     

Structural and Magnetic Properties of Codoped ZnO based Diluted Magnetic Semiconductors

Zn1-xCoxO （x = 0.01, 0.02, 0.05, 0.10 and 0.20） diluted magnetic semiconductors are prepared by the sol-gel method. The structural and magnetic properties of the samples are studied using x-ray diffraction （XRD）, extended x-ray absorption fine structure （EXAFS） and superconducting quantum interference device （SQUID）. The XRD patterns does not show any signal of precipitates that are different from wurtzite type ZnO when Co content is lower than x = 0.10. An EXAFS technique for the Co K-edge has been employed to probe the local structures around Co atoms doped in ZnO powders by fluorescence mode. The simulation results for the first shell EXAFS signals indicate that Zn sites can be substituted by Co atoms when Co content is lower than x = 0.05. The SQUID results show that the samples （x 〈 0.05） exhibit clear hysteresis loops at 300K, and magnetization versus temperature from 5 K to 350K at H = 100 Oe for the sample x = 0.02 shows that the samples have ferromagnetism above room temperature. A double-exchange mechanism is proposed to explain the ferromagnetic properties of the samples.     

Structure of nanosize bimetals Fe-Co and Fe-Ni

The phase composition and structural features of nano-size powders of Fe-Co and Fe-Ni systems synthesized by reducing the metal salts from strongly alkaline aqueous solutions are investigated by XAFS (XANES/EXAFS) and X-ray diffraction methods by using the synchrotron radiation (EXAFS spectrometer and diffractometer of Siberian SR Center) in combination with ordinary X-ray diffraction methods by using DRON-3.0 and Bruker D8 Advance diffractometers.     

Nanoresolution interface studies in thin films by synchrotron x‐ray diffraction and by using x‐ray waveguide structure

In the last years we performed several measurements with synchrotron radiation of several facilities to reveal interesting interface phenomena on the nanoscale. We used both x‐ray diffraction [1] , [2] (XRD) and spectrometry techniques. In this paper, we briefly summarize the results obtained from diffraction measurements, which lead us to our recent grazing incidence x‐ray fluorescence analysis (GIXRF) and extended x‐ray absorption fine structure (EXAFS) experiments. We show how a combination of experimental methods of GIXRF analysis and EXAFS spectroscopy in fluorescence detection with x‐ray standing waves (XSW) technique was applied for the depth profiling of a‐Si/Co/a‐Si layers with nanometer resolution to monitor the growth of CoSi intermetallic phase. The investigated layers were placed into the waveguide structure formed by two Ta films to increase sensitivity and accuracy of the measurements. Copyright © 2009 John Wiley & Sons, Ltd.     

A structure refinement strategy for NMR crystallography: an improved crystal structure of silica-ZSM-12 zeolite from 29Si chemical shift tensors

A strategy for performing crystal structure refinements with NMR chemical shift tensors is described in detail and implemented for the zeolite silica-ZSM-12 (framework type code MTW). The 29Si chemical shift tensors were determined from a slow magic-angle spinning spectrum obtained at an ultrahigh magnetic field of 21.1T. The Si and O atomic coordinate parameters were optimized to give the best agreement between experimentally measured and ab initio calculated principal components of the 29Si chemical shift tensors, with the closest Si-O, O-O, and Si-Si distances restrained to correspond with the distributions of the distances found in a set of single-crystal X-ray diffraction (XRD) structures of high-silica zeolites. An improved structure for the silica-ZSM-12 zeolite, compared to a prior structure derived from powder XRD data, is obtained in which the agreement between the experimental and calculated 29Si chemical shift tensors is dramatically improved, the Si-O, O-O, and Si-Si distances correspond to the expected distributions, while the calculated powder XRD pattern remains in good agreement with the experimental powder XRD data. It is anticipated that this "NMR crystallography" structure refinement strategy will be an important tool for the accurate structure determination of materials that are difficult to fully characterize by traditional diffraction methods.     

High Pressure X-Ray Absorption and Diffraction Study of InAs

We have performed X-ray absorption (XAS) and diffraction (XRD) measurements at high pressure on samples of powdered InAs, up to 50 and 80 GPa, respectively. In the lower pressure range, our data are consistent with the following structural sequence: Zincblende M NaCl M Cmcm . The first order transition from the semiconducting Zincblende phase to the metallic NaCl phase is clearly seen by the shift in the absorption onset at the As K-edge and the strong modifications of the extended X-ray absorption fine structure (EXAFS) due to the changes in the local structure from a 4-fold to a 6-fold coordinated environment. XAS shows the high pressure phase to be locally site-ordered. The diffraction data, analized by Rietveld fitting, gives a volume discontinuity of j V/V 0 ～0.18 for the first order transition. There is no apparent volume discontinuity associated to the NaCl M Cmcm transition.     

On the state of iron in a clinoptilolite

The characterization of an iron-containing natural zeolitic sample from the deposit of Tasajeras (Cuba) has been carried out by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS),⁵⁷Fe Mössbauer spectroscopy and Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The results show that iron is mainly located (ca. 96%) as Fe³⁺ in an octahedral site of the clinoptilolite framework. No evidence of tetrahedrally coordinated Fe³⁺ was found. The remaining 4% Fe is located as Fe²⁺ in an extraframework octahedral site, probably as a solvated ion, within the clinoptilolite structure.     

Variations of Ag bonding distances in the AgBr1−xIx solid-solution with rock-salt type structure by X-ray and EXAFS analyses

The local structure of the AgBr_1−xI_x rock-salt type solid-solution (0≤×≤0.4) was investigated by both EXAFS and single crystal X-ray diffraction. The first nearest neighbor distances from Br to Ag, and those from Ag to Br in the solid-solution can be determined from EXAFS method. Because Ag⁺ surrounded by both Br⁻ and I⁻ ions is locally attracted to Br⁻, which has larger effective negative charge than I⁻, the Ag-Br distances gradually decrease with AgI content. There are observed systematic changes in both Br K- and Ag K-edge XANES spectra with increasing AgI content in connection with the change of the local structure in the solid-solution. The Br and I ions are distributed at random over the 4(a) sites of space group Fm3m without forming clusters. Both cation and anion are displaced from the lattice site because the Ag-Br and Ag-I distances in the solid-solution are close, respectively, to the distances in the pure rock-salt type AgBr and a hypothetical rock-salt type AgI. The particular increase in temperature factors by X-ray diffraction results from the static displacements of both cations and anions from the normal octahedral site. A large enhancement of ionic conductivity in AgI rich region will be ascribed to an increase in the concentration of the Frenkel defect caused by changes in local structures in an equilibrium state.     

LaFe1－xCrxO3系列氧化物的EXAFS研究

采用固相反应法, 制备了钙钛矿结构氧化物LaFe_1－xCr_xO₃较宽范围内(x=0.0—0.7)的系列单相样品, 并测量了各样品的X射线衍射谱(XRD)和扩展X射线吸收精细结构(EXAFS)谱. 通过对XRD的分析样品均为钙钛矿结构正交相, 同时晶格常数随着掺杂量x的增加而减小. 通过对EXAFS的分析和研究得到在LaFe_1－xCr_xO₃氧化物中Fe-O键长和Fe-La键长随掺杂浓度x的变化, 发现Fe-La键长发生比较大的变化, 说明La在体系掺杂中对结构的稳定起到重要作用.     

遗传算法在EXAFS谱图解析中的应用

扩展Ｘ射线吸收精细结构（ＥＸＡＦＳ）谱是研究物质原子近邻结构和表面结构的有力工具。ＥＸＡＦＳ谱的解析通常采用标准样品比较法或最小二乘曲线拟合方法。但前者对标样的要求很高，而后者则参数初值难以确定，且结果有时不唯一。本文提出一种ＥＸＡＦＳ曲线拟合的新方法一遗传算法，并对单配位层Ｃｕ样品的ＥＸＡＦＳ谱图进行了解析，取得满意的结果。     

Diagnostics of gold-containing surgical-dressing materials with X-ray and synchrotron radiation

An analysis of biocompatible and antibacterial Au-gauze nanocomposites for medical purposes using X-ray and synchrotron radiation is conducted. The samples are produced by the modification of medical cotton gauze by Au organosol in isopropanol, which is synthesized via the metal-vapor method. The nanocomposites are examined with X-ray photoelectron spectroscopy, as well as with X-ray adsorption diffraction spectroscopy (EXAFS/XANES) and small-angle X-ray scattering using synchrotron radiation.     

Characterization of ternary and quaternary zirconias by XRD and EXAFS: result comparison and data modeling

X-ray diffraction (XRD) data and extended X-ray absorption fine-structure spectroscopy (EXAFS) data are compared for a zirconia-based solid solution such as ternary Er_0.05Y_0.10Zr_0.85O_1.925 (inert matrix) and quaternary Er_0.05Y_0.10Ce_0.10Zr_0.75O_1.925 (simulated inert matrix fuel where Ce is used instead of Pu). Average distances between the ions: metal–oxygen and metal–metal (for the 8 first shells of the cations) obtained by EXAFS are compared with values derived from the lattice parameter gained by XRD using a crystallographic formula derived for the fluorite-type solid solution. Data agreement makes comparison between atomic and crystallographic features very valuable for the characterization of these zirconia-based solid solutions (inert matrix fuel). The effect of the cation size of the dopants on the expansion of the crystallographic lattice is modeled and formal quantification of the lattice-parameter expansion as a function of ceria addition is derived. Received: 14 September 2000 / Revised version: 20 February 2001 / Published online: 20 June 2001     

EXAFS and diffraction

We discuss advantages and limitations of X-ray absorption fine structure (EXAFS), X-ray diffraction and anomalous X-ray diffraction as structural tools for ordered and (chemically and structurally) disordered solids.     

翡翠成分、结构和矿物组成的无损分析

利用便携式能量色散型X射线荧光(portable energy-dispersive X-ray fluorescence,PXRF)、外束质子激发X射线(external beam proton induced X-ray emission,PIXE)、X射线衍射(X-ray diffraction,XRD)和激光拉...