Investigation Of Local Structure Research Articles

Investigation on the local structure and properties of molten Li2CO3-K2CO3 binary salts by machine learning potentials

In recent years, (LinK1-n)2CO3 binary melts have been investigated as the promising electrolyte matrixes of the fuel cell. Many researchers moved to the investigation of local structure and properties of the melts. In this paper, machine learning interatomic potentials were developed based on first-principle datasets in order to research the local structure and properties of molten (LinK1-n)2CO3 (n = 0.4,0.5,0.6) binary salts. The trained machine learning potentials, which enable similar accuracy relative to DFT and high efficiency, can yield precise descriptions of microstructure and macro properties of Li2CO3-K2CO3 binary melts. The information of the microstructure evolution was analyzed through partial radial distribution functions, coordination numbers and bond angle distribution functions. It is observed that lithium cation exhibits more stable coordination and destroys the C-O ion pairs. Further, comparing the inter-ionic partial radius distribution function diagrams of binary melts and those of pure Li2CO3 and K2CO3 melts, the changing regularities of interatomic strength and arrangement were obtained. Macro properties including density, self-diffusion coefficients, thermal conductivity and viscosity at target temperature range were calculated by the potentials and MD simulations. The temperature effect and concentration effect in properties were explored. This work exhibits a thorough understanding of the local structure and properties of Li2CO3-K2CO3 melts and reveals the accuracy of machine learning potentials on lithium-potassium melts for the first time.

In-situ STS studies and first principles calculations on bare and Sn adsorbed UHV exfoliated WS2 layers

Abstarct. Two dimensional (2D) derivatives of tin (Sn) have obtained special deliberations recently due to practical realization of planar, as well as, buckled hexagonal lattice of Sn called stanene. However, it has been observed that proper choice of substrate is very important for growth of stanene like films owing to large core size of Sn that prefers sp 3 hybridization over sp 2. Transition metal dichalcogenides (TMDs) like MoS2 or WS2 with honey comb lattice structure seem to be promising substrate candidates for 2D growth of Sn. In the present work, we report mechanical exfoliation of few layers of WS2 under ultra-high vacuum (UHV) conditions and investigations of growth and local electronic structure by in-situ scanning tunneling microscopy (STM) and spectroscopy (STS) studies. Flat WS2 surface with honeycomb lattice structure in the atomic scale with a lattice constant of 0.34 nm is evident in the STM investigations, whereas, STS measurements reveal local density of states (LDOS) of WS2 with a bandgap of approximately 1.34 eV. Density functional theory (DFT) calculations performed by considering bulk WS2 reveal conduction and valence band states comprised of S p and W d at both sides of the Fermi energy (EF) and an indirect bandgap of 1.38 eV. Experimental observations upon Sn adsorption, reveal commensurate growth of Sn atoms on the sulfur `S’ sites with a buckling height of 40 ±10 pm. STS measurements exhibit local electronic structure of the Sn adsorbed surface with clear evidence of in-gap states. DFT calculations quantify the experimental results demonstrating `S’ sites as the most stable sites for the atomic adsorption of Sn with a buckling height of around 80 pm and reveal signature of in-gap hybridized states comprised of Sn p and W d orbitals.

Microwave-Assisted Coprecipitation Synthesis and Local Structural Investigation on NiO, β-Ni(OH)2/Co3O4 Nanosheets, and Co3O4 Nanorods Using X-ray Absorption Spectroscopy at Co-Ni K-edge and Synchrotron X-ray Diffraction.

Developing the most straightforward, cheapest, and eco-friendly approaches for synthesizing nanostructures with well-defined morphology having the highest possible surface area to volume ratio is challenging for design and process. In the present work, nanosheets of NiO and β-Ni(OH)2/Co3O4, and nanorods of Co3O4 have been synthesized at a large scale via the microwave-assisted chemical coprecipitation method under low temperature and atmospheric pressure. X-ray absorption spectroscopy (XAS) measurements, which comprises both X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques, have been carried out at Co and Ni K-edges to probe the electronic structure of the samples. Also, the local atomic structural, chemical bonding, morphological, and optical properties of the sample were systematically investigated using XAS, synchrotron X-ray diffraction (SXRD), Raman spectroscopy, FTIR, transmission electron microscopy (TEM), and UV–visible spectroscopy. The normalized XANES spectra of the β-Ni(OH)2/Co3O4 nanosheets show the presence of Ni2+ and a mixed oxidation state of Co. The disorder factor decreases from β-Ni(OH)2/Co3O4 to Co3O4 with increasing Co–O bond length. The SXRD pattern analyzed using Rietveld refinement reveals that NiO has a face-centered cubic phase, Co3O4 has the standard spinal structure, and β-Ni(OH)2/Co3O4 has a mixed phase of hexagonal and cubic structures. TEM images revealed the formation of nanosheets for NiO and β-Ni(OH)2/Co3O4 samples and nanorods for Co3O4 samples. FTIR and Raman spectra show the formation of β-Ni(OH)2/Co3O4, which reveals the fingerprints of Ni–O and Co–O.

In situ high-pressure nuclear magnetic resonance crystallography in one and two dimensions

Recent developments in in situ nuclear magnetic resonance (NMR) spectroscopy under extreme conditions have led to the observation of a wide variety of physical phenomena that are not accessible with standard high-pressure experimental probes. However, inherent di- or quadrupolar line broadening in diamond anvil cell (DAC)-based NMR experiments often limits detailed investigation of local atomic structures, especially if different phases or local environments coexist. Here, we describe our progress in the development of high-resolution NMR experiments in DACs using one- and two-dimensional homonuclear decoupling experiments at pressures up to the megabar regime. Using this technique, spectral resolutions of the order of 1 ppm and below have been achieved, enabling high-pressure structural analysis. Several examples are presented that demonstrate the wide applicability of this method for extreme conditions research.

Investigation of Local Structure and Enhanced Thermal Stability of Ir-Doped PdRu Nanoparticles for Three-Way Catalytic Applications

The local structure and thermal stability of newly synthesized PdRuIr and PdRu alloy nanoparticles (NPs) were studied using X-ray absorption fine structure spectroscopy (XAFS) and compared with those of Ru NPs. Pd K-edge XAFS reveals that a significant fraction of Pd segregates, forming metal NP clusters. In the PdRuIr NPs, a small fraction of Pd forms an alloy with Ir, whereas a majority phase is Ru–Ir alloy having the novel face-centered cubic structure. Apart from the distinct local surroundings, XAFS analysis revealed the presence of an anharmonic disorder in the PdRu and PdRuIr NPs. The previously observed enhanced thermal stability with Pd and Ir doping was investigated using temperature-dependent in situ XAFS. In the Ru NPs, an abrupt change in the near-edge features was observed at 673 K, which was gradually suppressed for PdRu and PdRuIr NPs. At this temperature, the dynamical fluctuations were more pronounced in the pure Ru NPs, helping to convert surface-adsorbed O2 into the volatile RuO4 phase, thereby leading to earlier evaporation of Ru. Dynamical fluctuation suppresses with alloying elements or gets extended to a higher temperature, helping to delay the RuO4 formation process and enhancing the thermal stability of the PdRu and PdRuIr NPs in increasing order.

The Spectrum of Crystallographic Misorientations of Intercrystalline Boundaries for BCC-HCP Phase Transformation in Additively Manufactured Ti-6Al-4V

Electron backscatter diffraction is a modern experimental method for local structure and texture investigation, which makes it possible to establish the presence and types of the various boundaries between the elements of the mesostructure such as low or high angle, special and interphase boundaries. Moreover, this technique can demonstrate the migration of boundaries during structural and phase transformations. This study estimated the possible spectrum of crystallographic misorientations of intercrystalline boundaries in additively manufactured titanium alloy Ti-6Al-4V using orientation microscopy and crystallographic calculations based on Burgers orientation relationship during β→α-transformation. The study has established that the boundaries between grains of α-phase are characterized by the misorientation angles of 11±2 °, 61±5 °, 89±3 °. The majority of high-angle boundaries are characterized by misorientation angles in the range of 57-65 °. The study also ascertained that the experimental spectrum of intercrystalline boundaries in the α-phase reveals the displacive nature of β→α-transformation in titanium alloys.

Local structural investigations of graphitic ZnO and reduced graphene oxide composite

Reduced graphene oxide (rGO) assisted two-dimensional (2D) graphitic ZnO (gZnO) have been prepared and characterized by Raman, FTIR, Cross-sectional high resolution transmission electron microscopy (HRTEM) and X-ray absorption spectroscopy (XAS) techniques comprising of X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Raman spectroscopy and FTIR measurements suggest formation of ZnO and the same has been corroborated by XANES measurements. HRTEM and polarization dependent XANES measurements with two different sample orientations confirm the formation of gZnO/rGO sandwiched layers. Density Functional Theory simulated relaxed initial structure of bilayers of gZnO sandwiched between successive rGO layers fits the EXAFS data reasonably well, supported by formation energy calculations which indicate better stability for samples having bilayers to a few layers of gZnO between rGO layers than with monolayer. These relaxed structures also help to understand the electronic structure contributing in XANES spectrum, with the help of ligand field theory.

Local Structure Investigations of Sequential Sorption of U and Fe on Polyacrylamide Hydroxamic Acid Resins.

Uranium- and iron-containing waste simulated effluent has been treated sequentially with a novel resin, viz., polyacrylamide hydroxamic acid (PAAHA). The motivation is to investigate the competitive interactions with transition metals during the removal of radiologically and chemically toxic uranium. The sequential sorption results indicate that the resin is more Fe selective compared to U and it retains more iron. X-ray absorption fine structure measurements, which comprise of both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques, have been carried out on the PAAHA resin at the Fe K-edge and U L3-edge to probe the change in the local coordination environment on sequential sorption of uranium and iron. EXAFS measurements conclude that the U-O distances and coordination are modified when the treatment sequences of U and Fe are interchanged, whereas the Fe local structure remains intact. The results obtained from EXAFS measurements have been verified by detail analysis of XANES data.

Local structure investigations of Sn and Mn doped in β-Ga2O3 by X-ray absorption spectroscopy

Sn-doped and Mn-doped β-Ga2O3 single crystals were grown by the floating zone method using SnO and MnCO3·nH2O as the dopant sources, respectively. We have succeeded in investigating the local structural features of Sn and Mn doped in β-Ga2O3 by X–ray absorption fine structure (XAFS) analysis. The XAFS analyses indicated the preference of Sn4+ at the octahedral sites in the β-Ga2O3 structure. On the other hand, the site preference for Mn is more complex, with most of the Mn present as Mn2+ substituting for Ga at the tetrahedral site. Further investigations using other spectroscopic techniques will be useful to clarify the effect and environmental structure of Mn.

Investigation of Local Structure of ZnO with High Doping Copper Concentration (≥13 %mole) Prepared by Co-Precipitation Method

Cu-doped ZnO (CZO) with Cu %mole of 0, 13, 14, and 15% have been synthesized by the co-precipitation method with controlled pH at 9. The diffraction pattern of CZO shows that a single phase of ZnO with wurtzite structure (w-ZnO) was achieved in the parent compound. In contrast, small fractions of the secondary phase of CuO monoclinic (m-CuO) were identified in the doped compounds. Rietveld-refinement on the X-Ray Diffraction (XRD) patterns reveals that the crystallite size of CZO is estimated in the range of 84 - 148 nm with instrumental correction factor and that CZO14 exhibits the most considerable fraction of m-CuO among the samples. Interestingly, lattice constants decrease by Cu doping. The effects of Cu doping on the valence state and the local structure were investigated by X-Ray Absorption Spectroscopy (XAS). Based on our analysis on both Cu K-edge and Zn K-edge XANES spectra, oxidation states of Cu and Zn ions are about +2 with no evidence of other valence states. Cu atom is likely to incorporate into wurtzite crystal lattice by occupying Zn sites in a small portion, and the doped compounds create a few oxygen vacancies.

Coexistence of local structural heterogeneities and long-range ferroelectricity in Pb-free (1−x)Ba(Zr0.2Ti0.8)O3−x(Ba0.7Ca0.3)TiO3 ceramics

Environmentally benign (1-x)Ba(Ti$_{0.8}$Zr$_{0.2}$)O$_3$-x(Ba$_{0.7}$Ca$_{0.3}$)TiO$_3$ (BZT-BCT) ceramics are promising materials due to their remarkable high piezoresponse [Liu and Ren, Phys. Rev. Lett. \textbf{103}, 257602 (2009)]. In this Letter, by focusing on local and average structure in combination with macroscopic electromechanical and dielectric measurements we demonstrate the structure property relationship in the tetragonal BZT-BCT ceramic. During high-temperature cubic to tetragonal phase transformation, polar nanoregions are manifested through the spontaneous volume ferroelectrostriction at temperatures below $\sim$ 477 K. Temperature-dependent local structural investigations across the Zr K edge extended x-ray absorption fine structure spectroscopy reveal an anomalous collaboration between the ZrO$_{6}$ and TiO$_6$ octahedra. These octahedra compromise their individuality during polarization development. The presence of domains of submicron size embedded inside the macroscopic ferroelectric regions below T$_{m}$, as well as their hierarchical arrangement, is observed by piezo-response force microscopy. Effects of the existence of the structural/polar heterogeneities below T$_{m}$ are observed also when polarizibilities of the poled and the unpoled samples are compared; the poled sample is found to be more susceptible to the electric field. In addition, by using electric field dependent x-ray diffraction studies we also show that this ceramic under field exhibits reduction of tetragonal distortion, which is consistent with earlier reports.

The elucidation of the alteration properties of BiFeO3 doped (K0.5Na0.5)NbO3 through local structure investigation

The alteration properties of BiFeO3 doped (K0.5Na0.5)NbO3 (KNN–BF) were investigated and focused on elucidating the origin of its modification. The crystal structure to have transformed from the initial orthorhombic to tetragonal shape at dopant amount x ≥ 0.025. Moreover, the XANES Fe K-edge analysis revealed the quadrupole transition 1s→3d, dipole transition 1s→4p, and edge energy E0 of samples were higher than those of Fe2O3 after which the oxidation state of Fe was found to be a mixture of 3+ and 4+. The defects, however, affected the properties by producing relaxor due to the polar nanoregions (PNRs) besides the presence of lattice dipole. Furthermore, the KNN was altered to ferromagnetic possessing Ms up to 0.0076 emu g−1 for x = 0.075 originating from the unpaired electron of Fe ions which was influenced by the interaction Fe3+-O2--Fe4+ and Nb5+-VO••-Fe3+/4+ in the B–O–B octahedron chain.

Modulating the Surface Ligand Orientation for Stabilized Anionic Redox in Li‐Rich Oxide Cathodes

AbstractAnionic redox chemistry is emerging as a key concept in the development of high‐energy lithium‐ion batteries, as it enables a nearly doubled charge storage capacity, aiding the development of high‐capacity batteries. However, the anionic reactivity is frequently irreversible from charge to discharge, leading to rapid decay of the capacity and voltage of batteries over long‐term cycling. Although the possibility of controlling the anionic redox reactions by tuning the geometric and electronic structures has recently been proposed, the implementation of this strategy is still a critical challenge. Herein, a strategy is proposed to improve the anionic redox reversibility of a model anionic redox active cathode material, Li1.2Ni0.13Co0.13Mn0.54O2, by tuning the surface ligand geometry via the growth of a lattice‐compatible spinel LiCoO2 coating layer on the particle surface. Detailed local structure and first principles investigations reveal that the shape and orientation of the octahedral layer in the host lattice are modified. Accordingly, a two‐band oxygen redox behavior is triggered in the ligand‐orientation‐regulated Li‐rich cathode, leading to enhanced reversibility, and thus, remarkably improved capacity and voltage retention over cycling. This study highlights the importance of controllable ligand orientation, carving a new path for the development and design of Li‐rich cathodes in the future.

0D Nanocrystals as Light‐Driven, Localized Charge‐Injection Sources for the Contactless Manipulation of Atomically Thin 2D Materials

A contactless charge‐injection scheme that allows the local and quasi‐permanent manipulation of atomically thin 2D materials, such as monolayer (1L‐)MoS2, over spatial extents of several tens of micrometers, is reported. The possibility to precisely position and localize the charge‐injection source to the micrometer scale post‐fabrication allows the investigation of local unperturbed electronic structure of the 2D material. Thanks to this novel approach, the important impact of sample inhomogeneity on the charge‐carrier percolation that occurs over the entire extent of the 2D flake and proliferates up to 40 μm away from the localized charge injection is elucidated. The apparent driving force for carrier relocation is the initial inhomogeneous electronic landscape of the 2D material. These studies demonstrate that local and contactless charge injection with submicrometer precision delivers an alternative route for charge injection and indicates that local 2D material electronic structure can serve as a key element for novel nanoscale device design.

Effect of Oxygen and Aluminum Incorporation on the Local Structure of GaN Nanowires: Insight from Extended X-ray Absorption Fine Structure Analysis

A thorough investigation of local structure, influencing the macroscopic properties of the solid, is of potential interest. We investigated the local structure of GaN nanowires (NWs) with different...

Local structure investigation of Co-Fe-Si-B ribbons by extended X-ray absorption fine-structure spectroscopy.

In the present work, extended X-ray absorption fine-structure (EXAFS) investigations of Co69FexSi21-xB10 (x = 3, 5, 7) glassy ribbons were performed at the Co K-edge. The magnitude of the first peak of the Fourier transforms of theEXAFS signals is found to increase monotonically with increasing Si concentrations indicating the formation of the localized ordered structure at the atomic scale. The Co-Si coordination number (CN) increases at the expense of the CN of Co/Fe. Smaller interatomic distances are observed in the glassy phase compared with that in the crystalline phase which promotes the stability of the glassy phase. Calculations of the thermodynamic parameter (PHSS), cohesive energy (EC) and the atomic radius difference (δ) parameter show that the alloy composition Co69Fe3Si18B10 has a good glass-forming ability (GFA) with the highest CN of Si compared with other compositions. A linear correlation of CN with that of the GFA parameter (PHSS) exists and the CN also plays a crucial role in the GFA of the glassy alloys. This parameter should be considered in developing different GFA criteria.

An investigation of local structures for 3d3, 3d5 and 3d7 ions doing in the layered LiCoO2 cathode materials

Doping transition metal ions in LiCoO2 batteries has been proved an efficient method to improve the electrochemical properties in experiment, which is deeply related with the distorted local structure of impurities ions. According to the observed EPR spectra, the distorted local structures for 3d3 (Mn4+), 3d5 (Fe3+) and 3d7 (Ni3+) ions in LiCoO2 batteries are theoretically studied based on the perturbation calculations of Spin Hamilton Parameters (g factors, hyperfine structure constants A and Zero-field splittings parameters D and E). By considering the Jahn-Teller effect and mismatch radius of above transition metal ions (TMs), the formed [MnO6]8-, [FeO6]9- and [NiO6]9- clusters in LiCoO2 exhibit various distorted symmetries compared with experimental single one, characterized by trigonal distortion parameter Δθ as well as rhombic distortion parameters ΔZ and Δϕ in the 3d3 center and the 3d5 center and tetragonal distortion parameter ΔZ in the 3d7 center. In addition, compared with asymmetrical signal of EPR spectra at 30K, the role of relatively high temperature for 100K is investigated by dynamic Jahn-Teller, making the isotropic EPR signal and regular octahedron for Ni3+ center. Comparing with the obtained structure properties of isolate-doped transition metal ion, the co-doped Mg in LiCoO2 makes the further elongated distortion of local structure. Based on the well fitted EPR parameters and obtained local environment of doped transition metal ions, the inactive of electrochemical properties of Mn4+ can be attribute to the largest crystal field (Dq) and the smallest difference with host Co3+ site. Therefore, a comprehensively study of the local structure may be helpful to understand and predict the electrochemical behaviors of batteries.

Local structural investigations of Fe-doped TiO2 amorphous thin films

The present study deals with the local structure of amorphous TiO2 and Fe-doped TiO2 thin films deposited on Si substrate using magnetron sputtering. The absence of long range order is confirmed by grazing incidence x-ray diffraction and the short range order is studied using x-ray absorption near edge structure (XANES) measurements at Ti, Fe and O K-edges and Fe and Ti L3-edge. The XANES provides understanding about the electronic transition induced from the short range ordering and dependence of electronic hybridization of the central Ti-p orbitals with the Ti-d orbitals. The XANES measurements also show that maximum Fe doping concentration allowed to replace Ti is 2 at.% and after that separate phase starts appearing, which is consistent with simulation by ab-initio multiple scattering theory based code FEFF9. Ellipsometry measurements show gradual decrease in band-gap energy upto 2 at.% Fe doping from pristine TiO2, however a drastic decrease in band-gap energy is observed at 4 at.% or higher doping concentration due to formation of other phases.

Investigation of local structures and electronic states of Sb-doped Mg2Si by fluorescence XAFS and HAXPES

To clarify the origin of the figure of merit in the thermoelectric material Mg2Si, we performed extended x-ray absorption fine structure (EXAFS) analysis and hard x-ray photoelectron spectroscopy (HAXPES). We elucidate the local structures and electronic states of Mg2Si, especially focusing on the contribution of doped Sb. EXAFS analysis revealed that Sb substituted Si and that the nearest neighbor distance expanded around Sb. Furthermore, HAXPES confirmed the formation of density of states near the Fermi level by co-doping with 0.5% Zn and 0.5% Sb. The comparison of the experimental and theoretical results suggested that the density of states at the Fermi level was due to the tail of the conduction band, and it was filled by the electrons provided by doped Sb. From a microscopic viewpoint, the results obtained in this study suitably explain why Sb doping increases electrical conductivity and decreases thermal conductivity in Mg2Si, as reported in a previous study.

Local structure investigation of WO<i><sub>x</sub></i> cluster modified on titanium-substituted hydroxyapatite for promoting charge separation under UV illumination

Local structure investigation of WO<i><sub>x</sub></i> cluster modified on titanium-substituted hydroxyapatite for promoting charge separation under UV illumination