Nb K-edge Research Articles

Structural Distortion in the Wadsley-Roth Niobium Molybdenum Oxide Phase Triggering Extraordinarily Stable Battery Performance.

Wadsley-Roth niobium oxide phases have attracted extensive research interest recently as promising battery anodes. We have synthesized the niobium-molybdenum oxide shear phase (Nb, Mo)13 O33 with superior electrochemical Li-ion storage performance, including an ultralong cycling lifespan of at least 15000 cycles. During electrochemical cycling, a reversible single-phase solid-solution reaction with lithiated intermediate solid solutions is demonstrated using in situ X-ray diffraction, with the valence and short-range structural changes of the electrode probed by in situ Nb and Mo K-edge X-ray absorption spectroscopy. This work reveals that the superior stability of niobium molybdenum oxides is underpinned by changes in octahedral distortion during electrochemical reactions, and we report an in-depth understanding of how this stabilizes the oxide structure during cycling with implications for future long-life battery material design.

Atomic-scale environment of niobium in ore minerals as revealed by XANES and EXAFS at the Nb K-edge

Abstract. The mineralogy of niobium (Nb) is characterized by multicomponent oxides such as AB2O6, A2B2O7, ABO4, and ABO3 in which Nb is incorporated in the B site. Such complex crystal-chemistry prevents their unambiguous identification in ore deposits such as hydrothermal rocks and laterites which exhibit complex and fine-grained textures. The understanding of the processes controlling Nb ore deposit formation in various geological settings is therefore limited, although Nb is a critical element. In this study, we use X-ray absorption spectroscopy (XAS) at the Nb K-edge to investigate the local atomic-scale structure around Nb in a large set of natural and synthetic minerals of geological and technological importance. Our X-ray absorption near-edge structure (XANES) data at the Nb K-edge show three major features of variable position and intensity and then can be related to the local distortion and coordination number of the Nb site. Shell-by-shell fits of the extended X-ray absorption fine structure (EXAFS) data reveal that the NbO6 octahedra are distorted in a variety of pyrochlore species. At least two distinct first shells of O atoms are present while reported crystallographic data yield regular octahedra in the same minerals. Next-nearest Nb–Nb distances in pyrochlore and Nb-bearing perovskite mirror a corner-sharing NbO6 network, whereas the two Nb–Nb distances in columbite are typical of edge- and corner-sharing NbO6 octahedra. Such a resolution on the Nb site geometry and the intersite relationships between the next-nearest NbO6 octahedra is made possible by collecting EXAFS data under optimal conditions at 20 K and up to 16 Å−1. The local structure around substituted Nb5+ in Fe3+, Ti4+, and Ce4+ oxides suffers major changes relative to the unsubstituted structures. The substitution of Nb5+ for Ti4+ in anatase leads to the increase in the interatomic distances between Nb and its first and second Ti4+ neighbors. The substitution of Nb5+ for Ce4+ in cerianite reduces the coordination number of the cation from eight to four, and the Nb–O bonds are shortened compared to Ce–O ones. In hematite, Nb5+ occupies a regular site, whereas the Fe3+ site is strongly distorted suggesting major site relaxation due to charge mismatch. The sensitivity of XANES and EXAFS spectroscopies at the Nb K-edge to the local site geometry and next-nearest neighbors demonstrated in this study would help decipher Nb speciation and investigate mineralogical reactions of Nb minerals in deposit-related contexts such as hydrothermal and lateritic deposits.

Solid solubility in the CeTi2O6–CeTiNbO6 system: A multi-element X-ray spectroscopic study

In order to investigate the limits of solid solubility between Ce-brannerite (CeTi2O6) and Ce-aeschynite (CeTiNbO6), materials in the system CeTi2–xNbxO6 have been produced by a solid state route and characterised by XRD and XANES at the Ce L3-, Ti K- and Nb K-edges, including Rietveld method refinements and linear combination fitting. Significant solid solubility was observed at the brannerite end, with near-single-phase brannerite observed for x = 0.2, 0.4, and only minor aeschynite observed where x = 0.6 which was identified as exceeding the limit of solubility of Nb. All Nb was present as Nb5+, with the substitution of Nb5+ into the brannerite structure permitted by the reduction of the same fraction of Ce4+ to Ce3+. This work expands the crystal chemistry of the titanate brannerites, with Ce-site oxidation states of less than 4+ being possible where sufficient charge-balancing species are available on the Ti-site.Graphical abstract

Local atomic structure of the high refractive index La2O3–Nb2O5–B2O3 glasses

High refractive glasses in the La2O3–Nb2O5–B2O3 (LNB) system were synthesized by the melt-quenching technique and correlations between their compositions and structural features were clarified. It was found that the refraction index of the LNB glasses is tunable from 1.71 to 1.98 by the variation of the Nb2O5 fraction from 5 to 30 mol%. The infrared spectroscopy analysis implies on the presence of three and four coordinated borate units, as well as six coordinated niobium atoms. The X-ray absorption (La L3-edge and Nb K-edge XANES and EXAFS) spectroscopy and total X-ray scattering results show that niobium atoms maintain octahedral oxygen coordination despite the wide variation of the Nb2O5 content, while average lanthanum coordination number is versatile and changes from ~8 to ~10. The interatomic distance values testify that the niobium octahedra in the glass network are connected only “by corners”. The stability of niobium local atomic structure implies that the main source of the changes in the optical properties of studied glasses is the variation of the Nb2O5 content. The deeper understanding of the local atomic structure of the high refractive index LNB glasses paves ways for the development of new glass wafers for cutting-edge augmented reality devices.

Niobium K-Edge X-ray Absorption Spectroscopy of Doped TiO2 Produced from Ilmenite Digested in Hydrochloric Acid.

Niobium doping of TiO2 creates a conductive material with many new energy applications. When TiO2 is precipitated from HCl solutions containing minor Nb, the Nb in solution is quantitatively deposited with the TiO2. Here, we investigate the structure of Nb doped in anatase and rutile produced from ilmenite digested in hydrochloric acid. Nb K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) are used to characterize the environment of 0.08 atom % Nb doped in TiO2. XANES shows clear structural differences between Nb-doped anatase and rutile. EXAFS for Nb demonstrates that Nb occupies a Ti site in TiO2 with no near neighbors of Nb. Hydrolysis of Ti and Nb from acid solution, followed by calcination, leads to a well dispersed doped material, with no segregation of Nb. Production of Nb-doped TiO2 by this method may be able to supply future demand for large quantities of the material and in energy applications where a low cost of production, from readily available natural resources, would be highly desirable.

The Local Structure and Metal-Insulator Transition in a Ba3Nb5-xTixO15 System.

The local structure of the filled tetragonal tungsten bronze (TTB) niobate BaNbTiO (x = 0, 0.1, 0.7, 1.0), showing a metal-insulator transition with Ti substitution, has been studied by Nb K-edge extended X-ray absorption fine structure (EXAFS) measurements as a function of temperature. The Ti substitution has been found to have a substantial effect on the local structure, that remains largely temperature independent in the studied temperature range of 80–400 K. The Nb-O bonds distribution shows an increased octahedral distortion induced by Ti substitution, while Nb-Ba distances are marginally affected. The Nb-O bonds are stiffer in the Ti substituted samples, which is revealed by the temperature dependent mean square relative displacements (MSRDs). Furthermore, there is an overall increase in the configurational disorder while the system with Nb 4d electrons turns insulating. The results underline a clear relationship between the local structure and the electronic transport properties suggesting that the metal-insulator transition and possible thermoelectric properties of TTB structured niobates can be tuned by disorder.

Determination of the structure of lithium niobosilicate glasses by molecular dynamics simulation with a new Nb-O potential

A partial charge empirical potential for the Nb-O pair has been developed based on existing parameters of other pairs in a Teter potential to enable molecular dynamics simulations of both lithium niobate crystal and lithium niobosilicate glasses. The developed potential is capable of describing structural features of lithium niobosilicate glasses in a wide composition range, including niobium coordination number and bond length, density, bond angle distribution, polyhedral distribution and fraction of bridging oxygen. The results obtained using this new potential show good agreement with experimental data of density and structure from Raman spectroscopy of lithium niobosilicate glasses and X-ray absorption spectroscopy near Nb K-edge.

Experimental investigation of the local environment and lattice distortion in refractory medium entropy alloys

EXAFS analysis of pure elements, binary and ternary equiatomic refractory alloys within the Nb-Zr-Ti-Hf-Ta system is performed at the Nb and Zr K-edges to analyze the evolution of the chemical local environment and the lattice distortion. A good mixing of the elements is found at the atomic scale. For some compounds, a distribution of distances between the central atom and its neighbors suggests a distortion of the structure. Finally, analysis of the Debye-Waller parameters shows some correlation with the lattice distortion parameter δ², and allows to quantify experimentally the static disorder in medium entropy alloys.

Effect of disorder on superconductivity of NbN thin films studied using x-ray absorption spectroscopy

The superconducting transition temperature (T C) of rock-salt type niobium nitride (δ − NbN) typically varies between 9 to 17 K and the theoretically predicted value of 18 K has not been achieved hitherto. The low T C in δ − NbN has been assigned to some structural disorder which is always present irrespective of the microstructure (polycrystalline or epitaxial), methods or conditions adopted during the growth of NbN thin films. In this work, we investigate the atomic origin of such suppression of the T C in δ − NbN thin films by employing combined methods of experiments and ab initio simulations. Sputtered δ − NbN thin films with different disorder were studied using the synchrotron-based N and Nb K-edge x-ray absorption spectroscopy techniques. A strong correlation between the superconductivity and the electronic structure reconstruction was observed. The theoretical analysis revealed that under N-rich growth conditions, atomic and molecular N-interstitial defects assisted by cation vacancies form spontaneously and results into a smeared electronic structure around Fermi-level. The role of electronic smearing on the T C is thoroughly discussed.

Anomalous Behavior in the Atomic Structure of Nb3Sn under High Pressure

In the present study, the local atomic structure of a Nb3Sn superconductor sample has been probed by X-ray absorption fine structure (XAFS) as a function of hydrostatic pressure (from ambient up to 26 GPa) using a diamond anvil cell set-up. The analysis of the Nb-K edge extended X-ray absorption fine structure (EXAFS) data was carried out combining standard multi shell structural refinement and reverse Monte Carlo method to provide detailed in situ characterization of the pressure-induced evolution of the Nb local structure in Nb3Sn. The results highlight a complex evolution of Nb chains at the local atomic scale, with a peculiar correlated displacement of Nb–Nb and Nb–Nb–Nb configurations. Such a local effect appears related to anomalies evidenced by X-ray diffraction in other superconductors belonging to the same A15 crystallographic structure.

First high-pressure XAFS results at the bending-magnet-based energy-dispersive XAFS beamline BL-8 at the Indus-2 synchrotron facility.

The static focusing optics of the existing energy-dispersive XAFS beamline BL-8 have been advantageously exploited to initiate diamond anvil cell based high-pressure XANES experiments at the Indus-2 synchrotron facility, India. In the framework of the limited photon statistics with the 2.5 GeV bending-magnet source, limited focusing optics and 4 mm-thick diamond windows of the sample cell, a (non-trivial) beamline alignment method for maximizing photon statistics at the sample position has been designed. Key strategies include the selection of a high X-ray energy edge, the truncation of the smallest achievable focal spot size to target size with a slit and optimization of the horizontal slit position for transmission of the desired energy band. A motor-scanning program for precise sample centering has been developed. These details are presented with rationalization for every step. With these strategies, Nb K-edge XANES spectra for Nb2O5 under high pressure (0-16.9 GPa) have been generated, reproducing the reported spectra for Nb2O5 under ambient conditions and high pressure. These first HPXANES results are reported in this paper. The scope of extending good data quality to the EXAFS range in the future is addressed. This work should inspire and guide future high-pressure XAFS experiments with comparable infrastructure.

Influence of Nb-doping on the local structure and thermoelectric properties of transparent TiO2:Nb thin films

Abstract Transparent n-type niobium-doped titanium dioxide thin films (TiO2:1.5 at.%Nb) with pronounced thermoelectric properties were produced from a composite Ti:Nb target by reactive magnetron sputtering. The thin films were comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, optical spectroscopy, electrical conductivity, and thermoelectric measurement techniques. The local structure of the thin films was investigated in detail by X-ray absorption spectroscopy at the Ti and Nb K-edges. A set of radial distribution functions were extracted from the simultaneous analysis of EXAFS data at two absorption edges using the reverse Monte Carlo method. It was found that Nb dopant atoms modify the local environment of the films, but their average structure remains close to that of the anatase phase. This conclusion is also supported by the ab initio simulations of XANES. A very high absolute Seebeck coefficient (S = 155 μV/K) for n-type TiO2 was achieved with Nb doping, yielding a maximum power factor and thermoelectric figure of merit of 0.5 mW m−1 K−2 and 0.18 at a temperature of 300 K, respectively, for a 150 nm thick film. From frequency-domain thermoreflectance experiments, a thermal conductivity value of 1.3 W m−1 K−1 was obtained for the optimized TiO2:Nb film.

The effects of swift Xe ion bombardment on the amorphous structure of a VITROPERM type alloy

Influence of swift Xe ion irradiation (ion energy of 11.1 MeV/u, ion fluences from 2.5 × 1012 to 1.0 × 1013 ions/cm2) on the local structural arrangement of a VITROPERM alloy is investigated using synchrotron-based X-ray diffraction, Fe and Nb K-edge X-ray absorption spectroscopy, and 57Fe Mössbauer spectroscopy techniques. The obtained data show an increase of structural disordering due to ion bombardment. However, no alterations in pairwise interatomic lengths are observed. The irradiation-induced structural modifications can be removed by an appropriate post-irradiation heat treatment. We suggest that the microscopic origin of changes induced by the swift heavy ions could be similar to the structural modifications caused by severe plastic deformation.

Identifying the local defect structure in (Na0.5K0.5)NbO3: 1 mol. % CuO lead-free ceramics by x-ray absorption spectra

The local defect structure around dopant atoms in 1 mol. % CuO doped (Na0.5K0.5)NbO3 lead-free ceramics was investigated by means of x-ray absorption spectra as compared with the local structure around the host Nb site. The Cu K-edge and O K-edge x-ray absorption near-edge structure spectra demonstrate divalent Cu ions that occupy the octahedrally coordinated Nb sites and also reveal the existence of oxygen vacancy VO¨ in the nearest neighboring around the Cu atom evidently. Moreover, the Cu and Nb K-edge extended x-ray absorption fine structure clearly suggests that the oxygen vacancies should be located at two O22 sites with the two longest Cu-O22 bond lengths, thus producing trimeric bent VO¨-CuNb″′-VO¨ defect complexes with a dipole moment PD parallel to the spontaneous polarization Ps, instead of dimeric CuNb″′-VO¨ and straight VO¨-CuNb″′-VO¨ defect complexes. This kind of special defect structure is also different from that observed in conventional Pb-based perovskite ferroelectrics in which only dimeric CuTi″-VO¨ defect dipoles were observed. Finally, the influence of the defect complexes on the macroscopic properties was specially discussed by taking into account the interaction between Ps and PD.

Local Structure Around Nb Site of a Potential Thermoelectric Material La1/3NbO3 from Temperature-Dependent Extended x-ray Absorption Fine Structure Spectroscopy

The effort to find thermoelectric materials suitable for different applications is an intense research topic of a large material science community. In this context, A-site-deficient La1/3NbO3, which shows an irreversible pressure-induced amorphization at above 15 GPa, has attracted recent attention. Here, we present a temperature-dependent Nb K-edge extended x-ray absorption fine structure (EXAFS) study of La1/3NbO3 in the range 77-500 K probing the Nb-O bond correlations. These results are compared with the Nb-O bond correlations in two related oxides NbO2 and Nb2O5. In comparison with NbO2 and Nb2O5, the Nb-O bond mean square relative displacements in La1/3NbO3 show much weaker temperature dependence revealing its enhanced spring constant. The “A” site deficiency in La1/3NbO3 may allow the oxygen atoms to preserve their local geometry and thus are less responsive to the external stimuli like temperature, which may be important in determining the thermal and electrical conductivity properties of this system.

A high pressure La K-edge X-ray absorption fine structure spectroscopy investigation of La1/3NbO3

ABSTRACTLa K-edge X-ray absorption spectroscopy has been used to elucidate the changes in the local electronic and lattice structure that occur in the A-site deficient double perovskite LaNbO up to 6 GPa. The pressure evolution of the oxygen dodecahedrum around the A-site has been examined. XANES (X-ray absorption near edge structure) data show modifications ascribed to the increase of bands overlapping as a consequence of the bond distance contraction, which has been directly probed by EXAFS (extended x-ray absorption fine structure) spectra. The La–O Debye Waller factors (DWFs) tend to increase whereas the La–Nb bond DWFs show only a tendency to decrease indicating the robustness of the crystal lattice structure, even in presence of the oxygen disordering. This permits the system to reverse back to its original conditions in this pressure range as evident from the measurements upon pressure release. The present results have been interpreted in the light of charge transfer related to the two-step reduction mechanism acting at the Nb site (with niobium ions passing from Nb to Nb) which also results in the elongation of the Nb–O bond distances in the octahedra, in agreement with the Nb K-edge results reported earlier.

Feasibility of electron and hole injection in heavily doped strontium barium niobate (SBN50) Sr0.5Ba0.5Nb2O6 for thermoelectric applications

Undoped and heavily doped (K, Y, Zr, Mo) strontium barium niobate Sr0.5Ba0.5Nb2O6 (SBN50) materials have been prepared by co-precipitation. X-ray diffraction shows the formation of a single-phase product and that 10% and 12.5% of the Nb sites can be occupied by Zr and Mo, respectively. K can enter 40% of the Sr sites, while the maximum Y substitution is also around 40%. The starting stoichiometry is effective in driving the substitutions to the desired sites. X-ray Absorption Spectroscopy (XAS) at the Nb-K edge shows the presence of Nb(V) independent of doping. A pre-edge 1s-4d transition surprisingly indicates the hole injection with Y doping and the electron injection with Zr doping. Chemical reduction does not affect the stability of the structure, except for a small decrease of maximum Y solubility, while the Nb(V) oxidation state and the XAS pre-edge feature are unmodified. The oxidized samples are insulators, the reduced samples show electrical conductivity, and doping significantly enhances thermopower and electrical conductivity. The Y doped sample shows a power factor ∼30 times larger than that of the undoped sample.

Synthesis−Structure–Function Relationships of Silica-Supported Niobium(V) Catalysts for Alkene Epoxidation with H2O2

Many industrially significant selective oxidation reactions are catalyzed by supported and bulk transition metal oxides. Catalysts for the synthesis of oxygenates, and especially for epoxidation, have predominantly focused on TiOx supported on or co-condensed with SiO2, whereas much of the rest of Groups 4 and 5 have been less studied. We have recently demonstrated through periodic trends using a uniform molecular precursor that niobium(V)-silica catalysts reveal the highest activity and selectivity for efficient utilization of H2O2 for epoxidation across all of Groups 4 and 5. In this work, we graft a wide range of Nb(V) precursors, spanning surface densities of 0.07–1.6 Nb groups nm–2 on mesoporous silica, and we characterize these materials with UV–visible spectroscopy and Nb K-edge XANES. Further, we apply in situ chemical titration with phenylphosphonic acid (PPA) in the epoxidation of cis-cyclooctene by H2O2 to probe the numbers and nature of the active sites across this series and in a set of relat...

Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3

Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb–O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb–O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb5+ towards Nb4+ above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb–O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at ∼14.5 GPa.

Structural differences between Sb- and Nb-doped tin oxides and consequences for electrical conductivity

High surface area Nb and Sb-doped tin oxides are prepared by co-precipitation. The differences in conductivity are rationalised using HT-XRD, SSNMR and Nb K-edge XANES characterisation.