Chemical Speciation of Trace Zinc in Ordinary Portland Cement Using X-ray Absorption Fine Structure Analysis

Chemical change of trace zinc in ordinary portland cement (205.1 ppm) was investigated in hydration process using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Intensities of the peaks appearing at the same energy of ZnO in XANES spectra were decreased with cement hydration. The interatomic distances and the coordination numbers of the first and the second shells calculated from EXAFS spectra indicated that ZnO hydrolyzed to zincate ion [Zn(OH)₄]²⁻ with cement hydration keeping their fundamental structure of ZnO₄ tetrahedra.     

Formation of Gold Clusters on TiO2 from Adsorbed Au(CH3)2(C5H7O2): Characterization by X-ray Absorption Spectroscopy

Gold nanoclusters on TiO₂ powder were prepared from adsorbed Au^III(CH₃)₂(C₅H₇O₂) (dimethyl acetylacetonate gold(III)) and characterized by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies. The samples were tested as catalysts for CO oxidation at 298 K and atmospheric pressure and characterized by EXAFS and XANES with the catalysts in the working state. The XANES results identify Au(III) in the initially prepared sample, and the EXAFS data indicate mononuclear gold complexes as the predominant surface gold species in this sample, consistent with the lack of Au–Au contributions in the EXAFS spectrum. The mononuclear gold complex is bonded to two oxygen atoms of the TiO₂ surface at an Au–O distance of 2.16 Å. Treatment of this complex in He or in H₂ at increasing temperatures led to formation of metallic gold clusters of increasing size, ultimately those with an average diameter of about 15 Å. The data demonstrate the presence of metallic gold clusters in the working catalysts and also show these clusters alone are not responsible for the catalytic activity.     

Incorporation of Cr in the passive film on Fe from chromate solutions

The uptake of Cr species from chromate solutions by Fe has been studied using X-ray absorption near edge structure (XANES). The objective of the investigation was to compare XANES with radioactive tracer techniques used by Brasher et al. Cr(III) was detected on the passive iron surface. The amount of Cr(III) was increased by cathodic polarization and decreased by anodic polarization. This demonstrated that the uptake of Cr(III) was the result of cathodic processes and was not a direct result of the growth of the passive oxide film. Cr(VI) was only found after Fe was exposed to a saturated dichromate solutions for extended periods indicating that Cr(VI) was not strongly absorbed on the passive film.     

Structural studies of a ZrO2–CeO2 doped system

The local structure around Zr, Ce and dopant atoms (Fe and Ni) in the ZrO₂–CeO₂ system investigated by X-ray absorption spectroscopy (XAS) is reported to better understand the tetragonal phase stabilization process of zirconia. The first coordination shell around Zr atoms is not sensitive to the introduction of dopants or to an increase in the ceria content (from 12 to 20 mol%). Ce ions maintain the eight-fold coordination as in CeO₂, but with an altered bond distance. The formation of vacancies resulting from reduction of Ce atoms can be discarded, because XANES spectra clearly show that Ce ions are preferentially in a tetravalent state. XANES and EXAFS experiments at the Fe K-edge evidence that the local order around Fe is quite different from that of the Fe₂O₃ oxide. On the one hand, ab initio EXAFS calculations show that iron atoms form a solid solution with tetragonal ZrO₂. The EXAFS simulation of the first coordination shell around iron evidences that the substitution of zirconium atoms by iron ones generates oxygen vacancies into the tetragonal network. This is a driven force for the tetragonal phase stabilization process. For Ni doped samples, EXAFS results show that Ni–O mean bond length is similar to the distance found in the oxide material, i.e., NiO compound. Besides this result, no evidence of similar solid solution formation for Ni-doped systems has emerged from the EXAFS analysis.     

Characterization of Metal-Oxide Catalysts in Operando Conditions by Combining X-ray Absorption and Raman Spectroscopies in the Same Experiment

We have developed a new instrumental setup that combines simultaneous X-ray absorption spectroscopy, Raman spectroscopy and online mass spectrometry for operando studies of catalytic reactions. The importance of combining these techniques in the same experiment is demonstrated with the example of CO oxidation over nanoscale copper oxide catalysts supported on high surface area titanium oxide. X-ray absorption near edge structure (XANES) spectroscopy provides information on the charge state and local geometry of the catalytically active atoms. Extended X-ray absorption fine-structure (EXAFS) technique adds information about their local coordination environment. Raman spectroscopy adds sensitivity to crystallographic phase and long range order that both XANES and EXAFS are lacking. Together, these measurements enable simultaneous studies of the structural and electronic properties of all components present in metal-oxide catalysts. Coupled with online reactant and product analysis, this new setup allows one to elucidate the synergy between different components of a catalytic system and shed light on its catalytic activity and selectivity.     

An XANES study of carbides of molybdenum and tungsten

The X-ray absorption near edge structure (XANES) of molybdenum and tungsten compounds has been studied by using synchrotron radiation. Substantial difference in XANES features between metals and their carbides suggested significant difference in electronic structure between them. The shift in edge position indicated charge transfer from metal to carbon when a carbide is formed. In light of a modern band theory, the larger white line areas for carbides could be interpreted as due to some of the unoccupied d-states which are not measured by x-ray white line area.     

Effect of thermal history on high‐valence chromium ion dissolution in merwinite (3CaO·MgO·2SiO2)

Solubility and local structure of transmission elements in calcium silicate compounds has not been well understood. We investigate the local structure of chromium ions dissolved in merwinite (3CaO·MgO·2SiO₂) of a monoclinic crystal structure. The acceptance of doping elements into merwinite has not been reported before. We found that chromium ions are soluble in merwinite in air and that chemical valence of the dissolved Cr ions varies with annealing temperature. The absorption edge in the x‐ray absorption near edge structure (XANES) of Cr‐doped merwinite indicated that octahedrally coordinated Cr³⁺ ions were mainly formed when annealed at 1673 K in air. A pre‐edge peak was also detected, indicating the existence of tetrahedrally coordinated high‐valence Cr ions. Conversely, through annealing of merwinite at 1123 K in air, tetrahedrally coordinated Cr⁶⁺ ions were found to be the main form of chromium. XANES spectra simulated by first‐principle calculations were used to explain the structural features in the observed spectra. We propose the coexistence of Cr³⁺ ions in octahedral Mg²⁺ sites and high‐valence Cr ions in tetrahedral Si⁴⁺ sites. In addition, a change in the chromium ion oxidation state in tetrahedral coordination sites was suggested by XANES spectroscopy of Cr‐doped merwinite synthesized at 1673 K and reannealed at 1123 K.     

XANES Determination of Chromium Oxidation States in Glasses: Comparison With Optical Absorption Spectroscopy

The oxidation state of chromium in glasses melted in an air atmosphere with and without refining agents was investigated by Cr K-edge X-ray absorption near-edge structure (XANES) and optical absorption spectroscopy. A good agreement in the relative proportion of Cr(III) and Cr(VI) is obtained between both methods. We show that the chemical dependence of the absorption coefficient of Cr(III) is less important in XANES than in optical absorption spectroscopy. The comparison of optical absorption and XANES spectra of glasses melted under different conditions provides an indirect assessment of the molar extinction coefficient of Cr(VI) in glasses.     

Formation Mechanisms of Tetragonal Barium Titanate Nanoparticles in Alkoxide–Hydroxide Sol-Precipitation Synthesis

The early stage of barium titanate (BaTiO₃) nanoparticle formation is investigated by in situ X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) using synchrotron radiation. BaTiO₃ nanoparticles are synthesized via dissolution of barium hydroxide octahydrate and hydrolysis of titanium (IV) isopropoxide in isopropanol. In the course of raising the temperature of the alkoxide–hydroxide mixture solution to 80°C, in situ synchrotron XRD reveals that BaTiO₃ nanocrystals smaller than 6 nm begin to nucleate at 50°C without intermediate TiO₂ anatase formation, and Ti K edge absorption spectra also confirm the formation of corner-sharing TiO₆ octahedra at 60°C. The average size of BaTiO₃ precipitates increases to about 7.5 nm at 80°C. The synthesized nanopowders show an anomalously high tetragonality according to the Rietveld refinement of synchrotron XRD data.     

In situ X-ray absorption spectroscopic study for the electrochemical delithiation of a cathode LiFe0.4Mn0.6PO4 material

The electronic and local atomic structural characterization of a promising cathode material, LiFe_0.4Mn_0.6PO₄, for a lithium rechargeable battery was performed by in situ X-ray absorption fine structure (XAFS) on both Mn and Fe K-edges. Upon delithiation, the X-ray absorption near edge structure (XANES) spectra analysis showed that the Fe²⁺/Fe³⁺ electrochemical reaction was two times faster than that of Mn²⁺/Mn³⁺. The Fe and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectra were effectively altered with different spectral behaviors for the local atomic structure near Fe and Mn during delithiation. Alternatively, the EXAFS spectra of LiFePO₄ changed significantly and those of LiMnPO₄ were constant through all delithiations for the corresponding reference materials of LiFePO₄ and LiMnPO₄. The present study with XAFS characterization demonstrates that initially delithiated Fe-rich domains at 3.5 V can promote more effective local structural change of the neighboring Mn-rich domains during the next second plateau at 4.1 V, which can ease delithiation in the Mn-rich domains through more flexible reaction of the local structure in the Mn octahedra.     

Preparation and characterisation of LiFePO4 ceramic powders via dissolution method

Various LiFePO₄ (LFP) powders with natural ironstone as a base material were prepared using the dissolution method. They were synthesised using different (a) calcination temperatures, (b) milling times, and (c) Cu doping concentrations. X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) were conducted to determine the purity, grain and crystallite morphology, and crystalline and local structure of the phases formed, respectively. According to the XRD data, LFP can be produced using the aforementioned variations, and no other phases were found. The TEM images showed that the LFP size can be reduced from 200 nm to 60 nm by milling. The SEM images confirmed the nanometric characteristics of the milled powder and also the effect of calcination temperature on growing the particle sizes. The EDX analysis further reinforced that the samples’ atomic fractions were relatively compatible with LFP to explain the synthesised products’ purity. Analysis of the Fe K-edge XANES data showed that the samples’ oxidation number of Fe for all samples was 2+ with 6 coordination numbers, which corresponded to the oxidation and coordination number of Fe in LFP. The EXAFS Fe K-edge analysis demonstrated that slightly increasing the temperature increased the distance between the absorbing Fe atom and its nearest neighbouring atom but milling reduced it. The XAS analyses, therefore, confirm that all synthesised samples contain only LFP. A preliminary electro-chemistry test showed that these materials are promising candidates for cathodes in LFP-based batteries.     

New frontiers in X-ray spectroscopy in heterogeneous catalysis: Using Fe/ZSM-5 as test-system

We have applied a number of novel X-ray spectroscopic tools to Fe/ZSM-5 systems. Fe/ZSM-5 can be considered as an ideal test-system for the characterization techniques in heterogeneous catalysis. The existence of a large range of sites and structures creates a good testing ground to determine which experimental tools are able to resolve such complex system. In situ soft X-ray absorption provides important information on the valence and electronic structure of iron during treatments, with a time scale down to 30 s. Kβ-detected XANES yields unprecedented resolution for pre-edge structures and using hard X-rays can be used under any condition and treatment, including high-pressures. It can be expected that both in situ soft X-ray absorption and Kβ-detected XANES become ‘standard’ tools for catalysis research, similar to traditional XANES and EXAFS today. The X-MCD is also used in this paper but it will probably remain a rather specialized technique in the field of heterogeneous catalysis. Further new developments for catalysis characterization are for all to be expected from X-ray spectro-microscopy, where one will have the possibility to perform the in situ soft X-ray absorption and Kβ-detected XANES experiments with nanometer size spatial resolution.     

Transition Elements and Nucleation in Glasses Using X-ray Absorption Spectroscopy

Selected results on the environment around Zr, Ti, and Ni in glasses and glass-ceramics using X-ray absorption spectroscopy (XAS) are presented to illustrate how this technique can provide information on the nucleation/crystallization processes. These elements actively participate to nucleation and, additionally, some of them bring new optical properties to the material. We show that extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) information, at K-edge or L_2,3-edges, can give short and medium range structural and bonding information. Nucleation activity of transition elements cannot be concluded from their local environment within the investigated parent glasses (at least for Zr and Ti, the main nucleating agents). On the contrary, medium range organization is important to understand nucleation processes with the evidence of heterogeneities or structural fluctuations that can be directly related to the first crystallizing phases. New developments in the spatial resolution or in situ high temperature measurements show the utility of the XAS technique with environmental changes around transition elements that can be detected prior to macroscopic crystallization. This can be useful to determine whether a specific ion (e.g., Ni²⁺) enters the crystalline phase and in which site, allowing a better control of the temperature or crystallization kinetics to optimize the material properties.     

Donor doping of K0.5Na0.5NbO3 ceramics with strontium and its implications to grain size,phase composition and crystal structure

In this study, the particular effects of A-site donor doping, such as crystal-structure change, the secondary-phase formation and the grain-size decrease, in a lead-free piezoceramic material K_0.5Na_0.5NbO₃ (KNN) doped with Sr²⁺, were investigated. Extended X-ray absorption fine structure (EXAFS) analyses proved that Sr occupies the perovskite A-sublattice, and locally modifies the KNN monoclinic structure to cubic. Introducing Sr into the A-sublattice, as well as accounting for the charge-compensating A-site vacancies in the starting composition, causes increasing lattice disorder and microstrain, as determined from a Rietveld refinement of the synchrotron X-ray diffraction data. Above 2% Sr the system segregates the A-site vacancies in a secondary phase in order to release the chemical pressure, as revealed by Raman spectroscopy. All these effects result in an increasing number of low-angle grain boundaries that limit the grain growth and finally lead to a significant grain-size decrease.     

Structure and electrical behaviour in air of TiO2-doped stabilized tetragonal zirconia ceramics

The data obtained from X-ray absorption (XANES and EXAFS) were used to provide information on the environment of Ti atoms in the TiO₂-doped stabilized tetragonal zirconia solid solutions. The electrical conductivity of the Ti–YTZP ceramics decreases with increasing TiO₂ content. From the EXAFS results, i.e. Ti–O and Ti–Ti distances, the decrease in conductivity was attributed to the formation of two kinds of cation–oxygen vacancy associations with different diffusion dynamics, leading to a decrease in the global concentration of moving oxygen vacancies.     

XANES investigation of co-precipitated Fe and Cr fluorides catalytically active in heterogeneous dehydrochlorination

In this X-ray absorption near-edge structure (XANES) study we focused our interest on co-precipitated Fe and Cr fluorides. Compounds with a low Cr content are catalytically active in the dehydrochlorination of 1,1,1-trichloroethane. XANES reveals for these samples an incorporation of a modified CrF_3-x(OH)x pyrochlore structure into the β-FeF₃ host lattice and an electron-deficient Cr 3d orbital, which may act as a Lewis acid site in the catalytic process. This revised version was published online in July 2006 with corrections to the Cover Date.     

The interaction between molten gallium and the hydrocarbon medium induced by ultrasonic energy—can gallium carbide be formed?

Ultrasonic irradiation of molten gallium in organic liquids (decane, dodecane, etc.) results in dispersion of the gallium into nanometric spheres. These were examined by several analytical methods XRD, DSC, Raman and IR spectroscopy) as well as electron microscopy (SEM, TEM) and found to be composed of Ga and C. The DSC analysis indicates that the Ga has possibly reacted with carbon, while the Raman spectrum of the product demonstrates a strong additional peak that could not be identified. This work explores the possibility that the product is gallium carbide or another gallium‐carbon complex. To investigate the nature of the product, we performed detailed extended X‐ray absorption fine structure (EXAFS) and X‐ray absorption near‐edge structure (XANES) analyses. On the basis of DSC, IR, and Raman it appear to be formation of GaC, whereas the analysis by EXAFS and XANES demonstrated that the gallium is found to be in a higher reduced state (almost metallic), supported by carbon. The question that remains open in addition to the one related to the formation of galium carbide is whether a complex structure, including oxygen contamination is involved in the layers surrounding the Ga as indicated by the EXAFS results.     

Structural Relaxation around Substitutional Cr3+ Ions in Sapphire

The local structural arrangement of ions around a substitutional Cr³⁺ ion in sapphire (ruby) has been studied experimentally using extended X-ray absorption fine structure (EXAFS) in the vicinity of the Cr absorption edge. The findings are compared with an ionic model (Mott-Littleton) computation using two sets of pairwise potentials. Both the EXAFS results and the computations reveal that when Cr substitutes for an Al ion in sapphire, the surrounding ions relax to an arrangement similar to that for Cr in α-Cr₂O₃. Also, most of the structural relaxation is accommodated by the first shell of oxygen and aluminum ions around the substituted Cr³⁺ ion. The computations also indicate that with applied pressure (tensile and compressive) the ionic positions change self-similarly and in proportion to the macroscopic strain.     

Formation and Local Structure Analysis of High‐Valence Chromium Ion in Dicalcium Silicate

Dicalcium silicate (2CaO·SiO₂) is a typical silicate compound that exists even at elevated temperatures. Different types of elements can be dispersed in dicalcium silicate to form a solid solution phase. However, the dispersion behavior of transition elements that can display different ionic valences is not well understood. Herein, we investigate the local structure of chromium ions dispersed in dicalcium silicate of different phase states under inert and air atmospheres using Cr K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy and first‐principle calculations. The measured XANES spectra indicated that Cr ions exist as high‐valence states when dispersed in dicalcium silicate in air atmosphere. Specifically, Cr⁶⁺ ions were detected in γ‐dicalcium silicate, which was prepared by annealing a mixture of 2CaO·SiO₂ and Cr₂O₃ at 973 K in air atmosphere. In addition, the XANES spectra obtained via first‐principle calculations revealed that Cr ions, with high‐valence states between Cr⁴⁺ and Cr⁶⁺, in dicalcium silicate, occupy the tetrahedral Si⁴⁺ sites.     

In situ XAFS Characterization of Supported Homogeneous Catalysts

Heterogenization of homogeneous catalysts explores the cross-fertilization of homogeneous and heterogeneous catalysts to combine most of their advantages. The molecular dispersion of active sites in these materials limits the application of conventional spectroscopic techniques utilized for the characterization of heterogeneous catalysts. The X-ray absorption spectroscopy is the most suitable tool to characterize the molecular species present in these catalysts because this technique is sensitive to short-range structural orders, element-specific and amenable to in situ studies. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) studies for selective examples of supported homogeneous catalysts are reviewed. Supported liquid phase catalysts (supported Wacker-type catalysts for CO oxidation), intercalated homogeneous catalysts, supported metal complexes for the olefin polymerization and tethered homogeneous catalysts are included.