Edge XANES Research Articles

Magnetically engineering enhanced EMA property through high entropy transition metal ions within all-inorganic perovskite

Addressing challenges such as signal interference and crosstalk requires the development of new materials capable of electromagnetic absorption (EMA). In this study, we explored magnetically high-entropy engineering by incorporating transition metal ions into the B sites of all-inorganic CsPbBr3 perovskite. This approach yielded excellent EMA properties, including a minimum reflection loss of 75 dB at 10.2 GHz with a thickness of 2.5 mm and an effective bandwidth of 8.8 GHz. Fe, Co, Ni, and Mn ions were successfully introduced into the CsPbBr3 lattice using high-energy ball milling and the combustion method. Through rigorous characterization techniques such as Rietveld refinement of X-ray diffraction and Grazing-Incidence Wide-Angle Scattering patterns, we confirmed the presence of high-entropy phases. Additionally, we conducted comprehensive studies using Vibrating-sample magnetometer, L2,3 edge XANES, and Mossbauer spectra to investigate the magnetic polarization, spin states, and dipolar exchanges of the transition metal ions. The observed synergistic effects among the magnetic permeability, polarization, and magnetic loss of these ions underscored their role in enhancing the EMA performance of CsPbBr3.

RETRACTED: Experimental determination of ferric iron partitioning between pyroxene and melt at 100 kPa

Pyroxene is the principal host of Fe 3+ in basalt source regions, hosting 79 and 81% of the Fe 3+ in spinel and garnet lherzolite, respectively. In spinel peridotite, orthopyroxene (opx) and clinopyroxene (cpx) host 48% and 31%, respectively, of the total Fe 3+ . Yet the relationship between mantle mineralogy, pyroxene chemistry, and the oxygen fugacity ( f O2 ) recorded by mantle-derived basalts remains unclear. To better understand partitioning of Fe 3+ between pyroxene and melt we conducted experiments at 100 kPa with f O2 controlled by CO-CO 2 gas mixes between ∆QFM −1.19 to +2.06 in a system containing andesitic melt saturated with opx or cpx only. To produce large (100–150 μm), homogeneous pyroxenes, we employed a dynamic cooling technique with a 5–10 °C/h cooling rate, and initial and final dwell temperatures 5–10 °C and 20–30 °C super and sub-liquidus, respectively. Resulting pyroxene crystals have absolute variation in Al 2 O 3 and TiO 2 < 0.05 wt% and < 0.02 wt%, respectively. Fe 3+ /Fe T in pyroxenes and quenched glass were measured by Fe K -edge XANES. We used a newly developed XANES calibration for cpx and opx by selecting spectra with X-rays vibrating on the optic axial plane at 45 ± 5° to the crystallographic c axis. Values of D Fe3+ cpx/melt increase from 0.03 to 0.53 as f O2 increases from ∆QFM −0.44 to +2.06, while D Fe3+ opx/melt remains unchanged at 0.26 between ∆QFM −1.19 to +1.37. In comparison to natural peridotitic pyroxenes, Fe 3+ /Fe T in pyroxenes crystallized in this study are lower at similar f O2 , presumably owing to lower Al 3+ contents. Comparison to thermodynamic models implemented in pMELTS and Perple_X suggest that these over-predict the stability of Fe 3+ in pyroxenes, causing these models to underpredict the f O2 of spinel peridotites under conditions of basalt genesis.

Application of M&lt;sub&gt;V&lt;/sub&gt;-edge XANES to determination of U oxidation state in zircon

Application of M&lt;sub&gt;V&lt;/sub&gt;-edge XANES to determination of U oxidation state in zircon

Investigation of local structural and magnetic properties of discontinuous to continuous layer of Co at Co/MgO interface in MgO/Co/MgO trilayer structure

We investigate influence of oxygen migration in MgO/Co/MgO trilayer structure by varying Co and MgO layer thickness. To resolve Co/MgO interface structural and magnetic properties, we used near edge X-ray absorption spectra (XANES), X-ray absorption fine structure (XAFS) spectroscopy and Magneto-optical Kerr effect (MOKE) on MgO/Co/MgO trilayer structure. O K-edge XANES spectra show the variation in hybridization of Co 3d orbitals with neighboring O 2p orbitals as a function of Co layer thickness. Co L3 -edge XANES and Co K-edge XAFS results revealed the quantity of CoO formation as a function of Co layer thickness from discontinuous layer to continuous layer. Formation of cobalt oxide is mainly due to island formation of Co ≤ 10 nm layer and oxygen migration from MgO layer at interface via redox reaction to form CoO bonds. The oxygen migration is driven by imperfect stoichiometry of MgO at the Co/MgO interface. The formation of CoO layer influences the CoO orbital hybridization modifying in-plane magnetic anisotropy as a function of Co and MgO layer thickness. Higher coercivity (Hc) for lower thickness of Co layer confirms the formation of domain wall pinning. A model has been drawn to describe the interaction of Co layer with MgO layer at Co/MgO interface from discontinues to continuous region of Co thin film of magnetic tunnel junctions (MTJ)s, which may help to design high-performance spintronic devices.

Photocatalytic activity of electron-deficient and porous WO3 nanoparticles derived from thermal oxidation of bulk WC particles

Abstract Electron-deficient and porous WO 3 particles were prepared by the simple thermal oxidation of commercial bulk WC. The crystal structure of as-prepared WO 3 particles was monoclinic phases and its crystallinity and morphology were controlled by varying the calcination temperature. Small and interconnected WO 3 particles were divided and formed from bulk WC particles with increasing calcination temperature. The electronic structure of thermally oxidized particles was studied by W L III -edge XANES. Interestingly, as-prepared WO 3 samples were in an electron-deficient state (W +6−δ ). The photocatalytic performance of as-prepared samples was investigated in terms of oxygen production in AgNO 3 aqueous solution and decomposition of the organic dye, Rhodamine B. The photoelectrochemical and photocatalytic activity were correlated and the results were most favorable for WO 3 particles thermally oxidized at 700 °C for oxygen production and 600 °C for photocurrent production.

Structural Changes in Ce0.5Zr0.5O2−δ under Temperature-Swing and Isothermal Solar Thermochemical Looping Conditions Determined by in Situ Ce K and Zr K Edge X-ray Absorption Spectroscopy

Structural changes in an equimolar ceria–zirconia solid solution were determined from room temperature to 1773 K under typical reducing and oxidizing conditions in a reactor for the solar thermochemical dissociation of water or carbon dioxide in a two-step redox cycle. We report the first in situ X-ray absorption spectroscopy (XAS) measurements at both the Ce K and Zr K edges under the conditions of thermochemical carbon dioxide splitting and a temperature swing of 1773 to 1073 K and isothermal conditions at 1773 K. The shift in the Ce K absorption edge reveals quantitative information about changes in the electronic structure of cerium. The maximum extent of reduction at 1773 K was 53% ± 5%; about 9% ± 5% of the cerium atoms changed valence from 4+ to 3+ and vice versa during isothermal looping in a flow of argon and carbon dioxide, respectively. Zr K edge XANES indicated a transformation of the oxygen coordination of zirconia to a more centrosymmetric cubic geometry upon reduction. During isothermal cyc...

Vanadium K-edge XANES in vanadium-bearing model compounds: a full multiple scattering study.

A systematic study is presented on a set of vanadium-bearing model compounds, representative of the most common V coordination geometries and oxidation states, analysed by means of vanadium K-edge X-ray absorption near-edge spectroscopy calculations in the full multiple scattering (FMS) framework. Analysis and calibration of the free parameters of the theory under the muffin-tin approximation (muffin-tin overlap and interstitial potential) have been carried out by fitting the experimental spectra using the MXAN program. The analysis shows a correlation of the fit parameters with the V coordination geometry and oxidation state. By making use of this correlation it is possible to approach the study of unknown V-bearing compounds with useful preliminary information.

Copper Valence and Local Environment in Aluminophosphate Glass-Ceramics for Immobilization of High Level Waste from Uranium-Graphite Reactor Spent Nuclear Fuel Reprocessing

ABSTRACTCopper valence and environment in two sodium aluminophosphate glasses suggested for immobilization of HLW from reprocessing of spent fuel of uranium-graphite channel reactor (Russian AMB) were studied by XRD, SEM/EDX, XAFS and EPR. Target glass formulations contained ∼2.4-2.5 mol.% CuO. The quenched samples were predominantly amorphous. The annealed MgO free sample had higher degree of crystallinity than the annealed MgO-bearing sample but both them contained orthophosphate phases. Cu in the materials was partitioned in favor of the vitreous phase. In all the samples copper is present as major Cu2+ and minor Cu+ ions. Cu2+ ions form planar square complexes (CN=4) with a Cu2+-O distance of 1.93-1.95 Å. Two more ions are positioned at a distance of 2.76-2.86 Å from Cu2+ ions. So the Cu2+ environment looks like a strongly elongated octahedron as it also follows from the absence of the pre-edge peak due to 1s→3d transition in Cu K edge XANES spectra of the materials. Cu+ ions form two collinear bonds at Cu+-O distances of 1.80-1.85 Å. Thus average Cu coordination number (CN) in the first shell was found to be 2.7-3.0.

Synthesis and Characterization of MnCrO4, a New Mixed-Valence Antiferromagnet

A new orthorhombic phase, MnCrO4, isostructural with MCrO4 (M = Mg, Co, Ni, Cu, Cd) was prepared by evaporation of an aqueous solution, (NH4)2Cr2O7 + 2 Mn(NO3)2, followed by calcination at 400 °C. It is characterized by redox titration, Rietveld analysis of the X-ray diffraction pattern, Cr K edge and Mn K edge XANES, ESR, magnetic susceptibility, specific heat and resistivity measurements. In contrast to the high-pressure MnCrO4 phase where both cations are octahedral, the new phase contains Cr in a tetrahedral environment suggesting the charge balance Mn(2+)Cr(6+)O4. However, the positions of both X-ray absorption K edges, the bond lengths and the ESR data suggest the occurrence of some mixed-valence character in which the mean oxidation state of Mn is higher than 2 and that of Cr is lower than 6. Both the magnetic susceptibility and the specific heat data indicate an onset of a three-dimensional antiferromagnetic order at TN ≈ 42 K, which was confirmed also by calculating the spin exchange interactions on the basis of first principles density functional calculations. Dynamic magnetic studies (ESR) corroborate this scenario and indicate appreciable short-range correlations at temperatures far above TN. MnCrO4 is a semiconductor with activation energy of 0.27 eV; it loses oxygen on heating above 400 °C to form first Cr2O3 plus Mn3O4 and then Mn1.5Cr1.5O4 spinel.

Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view

N-donor ligands such as n-Pr-BTP (2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine) studied here preferentially bind An(III) over Ln(III) in liquid-liquid separation of trivalent ac-tinides from spent nuclear fuel. The chemical and physical processes responsible for this selectivity are not yet well understood. We present systematic comparative near-edge X-ray absorption structure (XANES) spectroscopy investigations at the Gd L3 edge of [GdBTP3](NO3)3, [Gd(BTP)3](OTf)3, Gd(NO3)3, Gd(OTf)3 and N K edge of [Gd(BTP)3](NO3)3, Gd(NO3)3 complexes. The pre-edge absorption resonance in Gd L3 edge high-energy resolution X-ray absorption near edge structure spectra (HR-XANES) is explained as arising from 2p3/2 → 4f/5d electronic transitions by calculations with the FEFF9.5 code. Experimental evidence is found for higher electronic density on Gd in [Gd(BTP)3](NO3)3 and [Gd(BTP)3](OTf)3 compared to Gd in Gd(NO3)3 and Gd(OTf)3, and on N in [Gd(BTP)3](NO3)3 compared to n-Pr-BTP. The origin of the pre-edge structure in the N K edge XANES is explained by density functional theory (DFT) with the ORCA code. Results at the N K edge suggest a change in ligand orbital occupancies and mixing upon complexation but further work is necessary to interpret observed spectral variations.

Arsenic speciation in synthetic gypsum (CaSO4·2H2O): A synchrotron XAS, single-crystal EPR, and pulsed ENDOR study

Gypsum (CaSO4·2H2O) is a major by-product of mining and milling processes of borate, phosphate and uranium deposits worldwide and, therefore, potentially plays an important role in the stability and bioavailability of heavy metalloids, including As, in tailings and surrounding areas. Gypsum containing 1900 and 185ppm As, synthesized with Na2HAsO4·7H2O and NaAsO2 in the starting materials, respectively, have been investigated by synchrotron X-ray absorption spectroscopy (XAS), single-crystal electron paramagnetic resonance spectroscopy (EPR), and pulsed electron nuclear double resonance spectroscopy (ENDOR). Quantitative analyses of As K edge XANES and EXAFS spectra show that arsenic occurs in both +3 and +5 oxidation states and the As3+/As5+ value varies from 0.35 to 0.79. Single-crystal EPR spectra of gamma-ray-irradiated gypsum reveal two types of arsenic-associated oxyradicals: [AsO3]2− and an [AsO2]2−. The [AsO3]2− center is characterized by principal 75As hyperfine coupling constants of A1=1952.0(2) MHz, A2=1492.6(2) MHz and A3=1488.7(2) MHz, with the unique A axis along the S–O1 bond direction, and contains complex 1H superhyperfine structures that have been determined by pulsed ENDOR. These results suggest that the [AsO3]2− center formed from electron trapping on the central As5+ ion of a substitutional (AsO4)3− group after removal of an O1 atom. The [AsO2]2− center is characterized by its unique A(75As) axis approximately perpendicular to the O1–S–O2 plane and the A2 axis along the S–O2 bond direction, consistent with electron trapping on the central As3+ ion of a substitutional (AsO3)3− group after removal of an O2 atom. These results confirm lattice-bound As5+ and As3+ in gypsum and point to potential application of this mineral for immobilization and removal of arsenic pollution.

Combining XANES, ICP-AES, and SEM/EDS for the study of phytate chelating treatments used on iron gall ink damaged manuscripts

Many historical documents written with iron gall inks are endangered by the corrosive effects of these inks. In this work, a combination of complementary analytical methods was used for the first time in order to study the “phytate” process which is used in conservation studios to stabilize damaged manuscripts. This process consists of an antioxidant treatment performed by means of a calcium phytate (CP) solution, followed by a deacidification treatment performed with a calcium carbonate (CC) solution. The antioxidant treatment capitalizes on the properties of myo-inositol hexaphosphoric acid (phytic acid) that inhibits iron through chelation. In order to use relatively low acidic solutions, the pH of the CP solution is increased up to values between 5 and 6, which is in the range of the CP precipitation threshold. This study was performed on laboratory samples made of paper impregnated with iron gall ink and artificially aged in climatic chambers. It aims to investigate how the CP precipitate impacts the efficiency of the treatment. Side effects, such as elemental losses and deposits, were measured by means of several analytical techniques (Fe–K Edge XANES, SEM/EDS, and ICP-AES). These measurements were crosschecked with a ready to use colour spot test made of bathophenanthroline impregnated paper. It appeared that the CP treatment should necessarily be followed by the deacidification treatment in order to achieve long term stability. The precipitation of CP in the treating solution does finally not impact the efficiency of the treatment despite the fact that it should theoretically lower the availability of phytate to chelate iron. A scenario is proposed to explain this point.

In Situ X-Ray Spectroscopy and Imaging of Battery Materials

electrode materials during continuous cycling. The XAS results, together with the electrochemical data and other characterization information, provide deep understanding of the electrochemical reaction mechanisms and guidance on material design for lithium ion batteries. Understanding of the redox chemistry and changes in structure during cycling is critical to design new cathode materials with superior properties for lithium ion batteries. Yoon et al. 9 studied the charge compensation mechanism of Li 1-x Co 1/3 Ni 1/3 Mn 1/3 O 2 cathode material, which shows higher energy density and better safety than LiCoO 2 . The metal K edge XANES and EXAFS results show that the major charge compensation at the metal site during charging is achieved by the oxidation of Ni 2+ ions, while the manganese ions and the cobalt ions remain mostly unchanged in the Mn4+ and Co3+ state. Metal L-edge XAS results show that Ni ions at the surface are oxidized to Ni3+ during charge, whereas Ni ions in the bulk are further oxidized to Ni4+ during charge. In addition, from O K-edge XAS results, it is concluded that a large portion of the charge compensation during charging is achieved in the oxygen site due to presence of Co in the material, which is caused by the overlap of Co3+: 3d t 2g band with the O 2: 2p band. LiFePO 4 is another promising candidate for cathode material due to its low cost and excellent safety characteristics. The P K-edge XAS was studied to investigate the electronic structure of the delithiated Li 1-x FePO 4 material, and it shows that the electrochemical delithiation of Li 1x FePO 4 results in the hybridization of P 3p states with the Fe 3d states. 10

Nitrogen speciation in fine and coarse clay fractions of a Cryoboroll - new evidence from pyrolysis-mass spectrometry and nitrogen K-edge XANES

Soil clay fractions are usually enriched in nitrogen (N), but the chemical identity of this N is largely unknown. Therefore, we investigated organic N in fine and coarse clay of a clay-rich Cryoboroll by Curie-point pyrolysis-gas chromatography/mass spectrometry (Cp Py-GC/MS), Pyrolysis-field ionization mass spectroscopy (Py-FIMS) and synchrotron-based nitrogen K-edge X-ray absorption near edge structure (N-XANES) spectroscopy. The Cp Py-GC-MS revealed 30 structurally different N-containing compounds, such as substituted pyridines, pyrroles; pyrazines, pyrazoles, imidazoles, quinolines, side-chain N-containing benzenes, and single compounds of substituted benzotriazole, purine and indole. These accounted for about 10% of peak area in the Py-GC chromatograms. The Py-FIMS and N-XANES spectra indicated interlayer-NH4+ and revealed pyridinic and nitrilic N compounds, but disagreed in the proportions of pyrroles. All three complementary methods confirmed to different extents previous wet-chemical data on N-fractions in these samples, and provided new evidence for about 30 to 40% non-proteinaceous N as major constituent of the so-called “unknown organic N” in soil. Key words: Soil clay, organic matter, pyrolysis-mass spectrometry, synchrotron, X-ray absorption, NEXAFS

Determination of Ti coordination from pre-edge peaks in TiK-edge XANES

The pre-edge peaks of Ti $K$-edge XANES have been widely used in determining Ti coordination in amorphous materials and in crystals despite the fact that coordination is not the only factor that the pre-edge peaks depend on. This work thoroughly examines the dependence of the shape of Ti $K$ pre-edge peaks on various geometrical parameters (coordination, symmetry, Ti-O bond length and bond angle) using distorted rutile $\mathrm{Ti}{\mathrm{O}}_{2}$ as models. We conclude that the greatest impact on the pre-edge peaks arises from a reduction in Ti-O bond length, although other parameters such as symmetry and coordination all have some effect.

NitrogenK-edge XANES – an overview of reference compounds used to identify `unknown' organic nitrogen in environmental samples

The chemical nature of soil organic nitrogen (N) is still poorly understood and one-third to one-half of it is typically classified as ;unknown N'. Nitrogen K-edge XANES spectroscopy has been used to develop a systematic overview on spectral features of all major N functions in soil and environmental samples. The absolute calibration of the photon energy was completed using the 1s --> pi* transitions of pure gas-phase N(2). On this basis a library of spectral features is provided for mineral N, nitro N, amino acids, peptides, and substituted pyrroles, pyridines, imidazoles, pyrazoles, pyrazines, pyrimidines and purine bases. Although N XANES was previously considered ;non-destructive', effects of radiation damage were shown for two compound classes and an approach was proposed to minimize it. This new evidence is integrated into a proposal for the evaluation spectra from environmental samples with unknown composition. Thus a basis is laid to develop N K-edge XANES as a complementary standard research method to study the molecular composition and ecological functions of ;unknown N' in soil and the environment.

The active and reusable catalysts in the benzylation of anisole derived from a heteropoly acid

Benzylation of anisole with benzyl alcohol was carried out with H 3PO 4–WO 3–Nb 2O 5-derived catalysts. The catalytic performance depended significantly on the calcination temperature. The catalyst calcined at 573–723 K exhibited low activity and poor reusability, and the formation of heteropoly acid (HPA), which is similar to 12-tungstophosphoric acid, was identified by infrared (IR) and X-ray diffraction (XRD) measurements. The catalysts calcined above 823 K were in essence inactive in the reaction due to the formation of crystalline WO 3 that originated from HPA. In contrast, optimum activity was realized for the catalyst calcined at 773 K, which could be readily reused after filtration. The acid property of H 3PO 4–WO 3–Nb 2O 5 was measured by means of NH 3 TPD and the IR spectra of adsorbed pyridine. An enhancement of weak acid sites was observed for the catalyst calcined at 773 K, accompanied by the simultaneous reduction in the acidity due to HPA. The Brønsted acid sites were dominant in H 3PO 4–WO 3–Nb 2O 5 calcined at 773 K. The partially decomposed HPA, which maintained the same local symmetry around W atoms as HPA, was observed with W-L 3 edge EXAFS as well as W-L 1 edge XANES. From these data, the active and insoluble species obtained by the calcination of H 3PO 4–WO 3–Nb 2O 5 at 773 K was ascribed to the intermediate species of HPA formed in the decomposition process.

Investigation of the metamagnetic transition in Y2Co7H6

The effects of hydrogen absorption on the crystalline and magnetic properties of the γ-phase Y2Co7H6 were examined by bulk magnetic measurements, neutron diffraction and X-ray absorption spectroscopy. An orthorhombic distortion of the unit cell occurs upon hydrogen insertion, accompanied by a reduction of the magnetic moment on Co and a decrease of the ordering temperature. Magnetic measurements indicate a metamagnetic transition occurring in the γ-phase hydride. The transition shows a broad hysteresis and the magnitude of the critical field is found to decrease with increasing temperature. The electronic structure of Co in Y2Co7 and Y2Co7H6 has been investigated by X-ray absorption spectroscopy. The observed decrease of the pre-peak intensities in the Co-K edge XANES spectra are related to the changes of the 4p–3d density of states upon hydrogen insertion. A comparative X-ray magnetic circular dichroism investigation at the Co-K edge has been carried out for Y2Co7 and Y2Co7H6. The observed XMCD signal enables us to propose that ferromagnetic ordering occurs in the γ-hydride.

In situ investigations of structure–activity relationships of a Cu/ZrO 2 catalyst for the steam reforming of methanol

Structure–activity relationships of a nanostructured Cu/ZrO 2 catalyst for the steam reforming of methanol (MSR) were investigated under reaction conditions by in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) combined with on-line mass spectrometry (MS). Temperature-programmed activation by reduction in hydrogen or by reduction in a mixture of methanol and water (feed) was studied by time-resolved Cu K edge XANES and TG/DSC/MS measurements. Small and disordered CuO particles were identified as the main copper phase present in the precursors. After extended time on stream and treatment at 673 K in hydrogen, no significant sintering of the copper particles or deactivation of the reduced Cu/ZrO 2 catalysts was detected, indicating a superior stability of the material. The initially low steam-reforming activity of the Cu/ZrO 2 catalyst after reduction in hydrogen could be significantly increased by a temporary addition of oxygen to the feed. This increased activity after oxidative treatment is correlated with an increasing amount of oxygen in the copper particles. 63Cu NMR studies detected only a minor degree of microstrain in the active copper phase of the Cu/ZrO 2 catalyst. The decreased reducibility of CuO/ZrO 2, the low degree of microstrain, and the correlation between the amount of oxygen remaining in the copper particles and the catalytic activity indicate a different metal support interaction compared with Cu/ZnO catalysts.

Nanostructured Ti−W Mixed-Metal Oxides: Structural and Electronic Properties

In this article, the structural and electronic properties of Ti-W binary mixed oxide nanoparticles are investigated by using X-ray diffraction, Raman, X-ray absorption spectroscopies (XAS; near edge XANES and extended EXAFS), UV-vis spectroscopy, and density functional calculations. A series of Ti-W binary oxide samples having W content below 20 atom % and with particle size between 8 and 13 nm were prepared by a microemulsion method. The atoms in these nanoparticles adopted the anatase-type structure with a/b lattice constants rather similar to those of the single TiO(2) reference and with a c cell parameter showing a noticeable expansion upon doping. Within the anatase structure, W occupies substitutional positions, while Ti atoms only suffer minor structural perturbations. A change in the W local order at first neighboring distance is observed when comparing samples having a W content below and above 15 atom %. Charge neutrality is mostly achieved by formation of cation vacancies located at the first cation distance of W centers. Upon addition of W to the TiO(2) structure, the Ti charge is not strongly modified, while changes in the W-O interaction appear to drive a modest modification of the W d-electron density throughout the Ti-W series. A combination of these geometrical and electronic effects produced Ti K- and W L(I)/L(III)-edge XANES/EXAFS spectra with distinctive features. UV-vis spectra show a nonlinear decrease of the band gap in the Ti-W solid solutions with a characteristic turning point at a W content of ca. 15 atom %. The relationship between local/long-range order and electronic parameters is discussed on the basis of these experimental results.