Investigation Of Local Structure Research Articles

High-Resolution Electron Microscopy Imaging of MOFs at Optimized Electron Dose

Local and high-resolution structural investigation of metal-organic frameworks (MOFs) is essential for understanding the role of defects and incorporated elements. In this paper, we characterize the structure of metalated versions...

Unleashed Remarkable Energy Storage Performance in Bi0.5K0.5TiO3‐based Relaxor Ferroelectrics by Local Structural Fluctuation

AbstractDielectric capacitors harvest energy through an electrostatic storage process, which enables an ultrafast charging‐discharging rate and ultrahigh power density. However, achieving high energy density (Wrec) and efficiency (η) simultaneously, especially when preserving them across a wide frequency/temperature range or cycling numbers, remains challenging. In this work, by especially introducing NaTaO3 into the representative ferroelectric relaxor of Bi0.5K0.5TiO3‐Bi0.5Na0.5TiO3 and leveraging the mismatch between B‐site atoms, we proposed a method of enhancing local structural fluctuation to refine the polar configuration and to effectively improve its overall energy‐storage performances. As a consequence, the ceramic exhibits an ultrahigh Wrec of 15.0 J/cm3 and high η up to 80 %, along with a very wide frequency stability of 10–200 Hz and extensive cycling number up to 108. In‐depth local structure and chemical environment investigations, consisting of atom‐scale electron microscopy, neutron total scattering, and solid‐state nuclear magnetic resonance, reveal that the randomly distributed A/B‐site atom pairs emerge in the system, leading to the evident local structural fluctuations and concomitant polymorphic polar nanodomains. These key ingredients contribute to the large polarization, minimal hysteresis, and high breakdown strength, thereby promoting energy‐storage performances. This work opens a new path for designing high‐performance dielectric capacitors via manipulating local structural fluctuations.

Unleashed Remarkable Energy Storage Performance in Bi0.5K0.5TiO3-based Relaxor Ferroelectrics by Local Structural Fluctuation.

Dielectric capacitors harvest energy through an electrostatic storage process, which enables an ultrafast charging-discharging rate and ultrahigh power density. However, achieving high energy density (Wrec) and efficiency (η) simultaneously, especially when preserving them across a wide frequency/temperature range or cycling numbers, remains challenging. In this work, by especially introducing NaTaO3 into the representative ferroelectric relaxor of Bi0.5K0.5TiO3-Bi0.5Na0.5TiO3 and leveraging the mismatch between B-site atoms, we proposed a method of enhancing local structural fluctuation to refine the polar configuration and to effectively improve its overall energy-storage performances. As a consequence, the ceramic exhibits an ultrahigh Wrec of 15.0 J/cm3 and high η up to 80 %, along with a very wide frequency stability of 10-200 Hz and extensive cycling number up to 108. In-depth local structure and chemical environment investigations, consisting of atom-scale electron microscopy, neutron total scattering, and solid-state nuclear magnetic resonance, reveal that the randomly distributed A/B-site atom pairs emerge in the system, leading to the evident local structural fluctuations and concomitant polymorphic polar nanodomains. These key ingredients contribute to the large polarization, minimal hysteresis, and high breakdown strength, thereby promoting energy-storage performances. This work opens a new path for designing high-performance dielectric capacitors via manipulating local structural fluctuations.

Investigation of local structure by X-ray absorption fine structure and magnetic properties of CoMn2O4 nanoparticles

Investigation of local structure by X-ray absorption fine structure and magnetic properties of CoMn2O4 nanoparticles

An Investigation of Local Structures and Spin Hamiltonian Parameters for Cu2+ in xBaO–(30–x)TeO2–10TiO2–58B2O3 Glasses

An Investigation of Local Structures and Spin Hamiltonian Parameters for Cu2+ in xBaO–(30–x)TeO2–10TiO2–58B2O3 Glasses

Effect of Heating/Cooling Rate on the Local Electronic Structure of Amorphous Calcium Carbonate

Here, in the impact of heating/cooling rate was investigated on the formation of amorphous calcium carbonate (calcite) during sol-gel synthesis by probing local electronic structure. The amorphous calcium carbonate was synthesized by annealing precursor at 400oC at different heating/cooling rates i.e., 1.5 and 3oC /min. X-ray diffraction studies revealed amorphous nature at both heating/cooling rates. Fourier transformed infrared spectroscopic measurements characteristics bands in the spectra of both materials. Near edge X-ray absorption fine structure measurements at Ca L-edge, C K-edge and O K-edge were utilized to reveal the associated changes in the local electronic structure during synthesis. Local electronic structure investigation using near edge X-ray absorption fine structure measurements shows onset of moisture absorption on the surface particles when kept in the open environment.

Investigation of local structure and phase recovery in an irradiated Nd2Zr2O7 pyrochlore

SHI irradiation-induced order–disorder transition in an Nd2Zr2O7 pyrochlore is observed by XRD and XAS measurements. The recrystallization of the irradiated phase was observed as a result of thermal annealing.

Local Structure in Sodium Antiperovskite Ionic Conductors

Antiperovskites, which can serve as solid state electrolytes, have recently received great attention due to their high ionic conductivity[1]. Compared to typical solid-state ionic conductors, Na3OCl antiperovskite exhibits a unique ionic conductivity behavior that deviates from a linear Arrhenius behavior, in which the ionic conductivity increases rapidly with increasing temperature[2,3]. Many different structural origins affecting the ion conduction mechanism in antiperovskite have been proposed using calculation, such as vacancy/dumbbell migration[4]. The lack of direct experimental local structural investigations makes it challenging to fully understand the structural origins for high ionic conductivity, even resulting in limitations in the development of material designs for good ionic conductors. Complicating their investigation, these materials are also extremely sensitive to air, preventing many structural studies.Here, local structural investigations of Na3OCl are performed using aberration corrected scanning transmission electron microscopy (STEM) to elucidate the atomistic mechanisms underlying its high ionic conduction. To avoid degradation in air, we use an inert gas transfer system that has several advantages. First, transfer in an inert gas environment without air/moisture exposure enables the sample to retain the on-stoichiometry. Second, both room temperature and cryo experiments are possible, which allows pristine structure investigation at application relevant temperatures. Beyond the environment, Na3OCl is also very electron beam sensitive. We will show that low-dose imaging methods, such as parallel beam electron diffraction and electron ptychography, can provide new insights and allow for direct imaging of the local structure. For example, diffuse electron scattering (scattering between the Bragg reflections) is used to investigate subtle differences resulting from local structure, atomic defects, and phonon dispersion relations through combination with electron scattering simulations and Molecular Dynamics (MD) using machine learned potentials. We will then demonstrate how electron ptychography can achieve deep sub-angstrom spatial resolution with low dose conditions and provide direct insights into the migration of Na-ions. Overall, the inert gas transfer system and low-dose diffraction and STEM ptychography enable direct imaging of local structures even for reactive and electron beam sensitive materials, such as antiperovskite electrolytes. The understanding of local structure related to the high ionic conductivity will be crucial for designing high-performance solid electrolytes.

Local structure investigation of Cr3+ doped KTP single crystals

Using superposition model (SPM), the crystal field (CF) parameters and zero field splitting (ZFS) parameters of Cr3+ doped KTP single crystals are determined The possible sites for Cr3+ ions in KTP with distortion are taken up for calculation. Considering local distortion the theoretical ZFS parameters are in good agreement with the experimental values. The optical energy values for Cr3+ in KTP are calculated with the help of CF parameters and CFA program. The results show that Cr3+ ions substitute at Ti4+ (2) sites in KTP single crystals.

Investigation of grain boundary and local structure of Sr-doped LLZO with high Li-ion conductivity

Investigation of grain boundary and local structure of Sr-doped LLZO with high Li-ion conductivity

Investigation of local structure and phase transformation in Ce-doped barium titanate and correlation with electrical properties

ABSTRACT BaTiO3-based materials are used as the replacement for lead-based perovskite materials for its wide dielectric applications. But the substitution of different doping elements in pure BaTiO3 drastically affects the microstructure, phase transition behavior and electrical properties. In the present work, local structure, phase transformation and dielectric behavior of BaCexTi1-xO3 (BCT) ceramics were studied for compositions x = 0.02, 0.05 and 0.1. A diffuse phase transition from orthorhombic to cubic via tetragonal in BCT with increasing Ce content was observed. An increase in particle size with Ce doping concentration was observed in FESEM images. Spherical and cuboid-shaped particle in the order of 80–150 nm was observed in transmission electron microscopic (TEM) images. RAMAN spectra confirm the tetragonal to cubic phase transition. Local structural and phase transformation behavior was obtained from laboratory-based PDF and XRD, respectively. Change in PDF was observed due to an increase in Ce doping. Dielectric properties decreased for Ce mole fraction of x = 0.1.

Synthesis of Free-Standing Pd-Ni-P Metallic Glass Nanoparticles with Durable Medium-Range Ordered Structure for Enhanced Electrocatalytic Properties.

Topologically disordered metallic glass nanoparticles (MGNPs) with highly active and tailorable surface chemistries have immense potential for functional uses. The synthesis of free-standing MGNPs is crucial and intensively pursued because their activity strongly depends on their exposed surfaces. Herein, a novel laser-evaporated inert-gas condensation method is designed and successfully developed for synthesizing free-standing MGNPs without substrates or capping agents, which is implemented via pulse laser-induced atomic vapor deposition under an inert helium atmosphere. In this way, the metallic atoms vaporized from the targets collide with helium atoms and then condense into short-range-order (SRO) clusters, which mutually assemble to form the MGNPs. Using this method, free-standing Pd40 Ni40 P20 MGNPs with a spherical morphology are synthesized, which demonstrates satisfactory electrocatalytic activity and durability in oxygen reduction reactions. Moreover, local structure investigations using synchrotron pair distribution function techniques reveal the transformation of SRO cluster connection motifs of the MGNPs from face-sharing to edge-sharing modes during cyclic voltammetry cycles, which enhances the electrochemical stability by blocking crystallization. This approach provides a general strategy for preparing free-standing MGNPs with high surface activities, which may have widespread functional applications.

Pd–Ni–P metallic glass nanoparticles for nonenzymatic glucose sensing

Metallic glass nanoparticles hold great promise as nonenzymatic glucose sensors due to their rich low-coordinated active sites and high biocompatibility. However, their non-periodic atomic structure and unclear structure-property relationship pose significant challenges for realizing and optimizing their sensing performance. In this work, Pd–Ni–P metallic glass nanoparticles with variable compositions were successfully prepared as nonenzymatic glucose sensors via a laser-evaporated inert-gas condensation method. The electrochemical tests show that the sensor based on Pd41·25Ni41·25P17.5 nanoparticles shows a wide linear detection range (0.003–1.31 ​mM), high sensitivity (516 ​μA ​mM−1 ​cm−2), and high stability (∼97.8% current retention after 1000 cycles). Local structural investigations using synchrotron pair distribution function and high-resolution microscopic techniques reveal a strong structural correlation within short-to medium-range orders in the Pd41·25Ni41·25P17.5 nanoparticles, which can be well retained after electrochemical cycling. These atomic-scale structural characteristics might be responsible for the high sensing performance. This study demonstrates the high applicability of Pd–Ni–P metallic glass nanoparticles as sensitive and stable non-enzymatic glucose sensors.

Protic amine/acid mixtures as solvents for the extraction of aqueous zinc salts: A mechanistic study

Mixtures based on trihexylamine and cyclic carboxylic acids (aromatic and non-aromatic) were used as solvents for the extraction of zinc salts from aqueous phases via liquid–liquid extractions. The anions of the zinc salts were chosen to represent a range of kosmo-/chaotropic characters, and their influence on the extractions was observed. The extraction studies were supplemented by investigation of local liquid structure through small-angle x-ray scattering (SAXS). The results indicate that extraction is strongly influenced by the Hofmeister effect, but the local liquid structure appears insensitive to anion kosmo-/chaotropic character. In contrast to similar extraction studies, the strength of the Hofmeister effect did not change according to the composition of the mixtures.

Local structural investigation of non-crystalline materials at high pressure: the case of GeO2 glass

Local structures play a crucial role in the structural polyamorphism and novel electronic properties of amorphous materials, but their accurate measurement at high pressure remains a formidable challenge. In this article, we use the local structure of network-forming GeO2 glass as an example, to present our recent approaches and advances in high-energy x-ray diffraction, high-pressure x-ray absorption fine structure, and ab initio first-principles density functional theory calculations and simulations. Although GeO2 glass is one of the best studied materials in the field of high pressure research due to its importance in glass theory and geophysical significance, there are still some long-standing puzzles, such as the existence of appreciable distinct fivefold [5]Ge coordination at low pressure and the sixfold-plus [6+]Ge coordination at ultrahigh pressure. Our work sheds light on the origin of pressure-induced polyamorphism of GeO2 glass, and the [5]Ge polyhedral units may be the dominant species in the densification mechanism of network-forming glasses from tetrahedral to octahedral amorphous structures.

A spherical harmonics method for processing anisotropic X-ray atomic pair distribution functions

In this work, a general spherical harmonics method for the extraction of anisotropic pair distribution functions (PDFs) is described. In the structural study of functional crystallized materials, there is an urgent need for investigation of local structures under the application of external stimuli, such as an electric field and stress. A well established technique for local structural studies is PDF analysis, but the extraction of X-ray PDF data is usually based on angular integrations of isotropic X-ray structure functions, which is no longer valid for the anisotropic responses of materials under orientation-dependent stimuli. Therefore, an advanced spherical harmonics method has been developed, to transform 2D X-ray total-scattering data into anisotropic PDF data on the basis of the 3D diffraction geometry and a Fourier transform. The electric-field-induced local structural change in PbZr0.54Ti0.46O3 ceramics is presented to demonstrate the effectiveness of this method.

Interplay of dopant and polarons in trifunctional semimagnetic semiconductor for supercapacitor applications: Local structure and electronic structure investigations

Diluted magnetic semiconductors (DMS), fractionally doped by magnetic ions, are peculiar, and a single semiconductor effectively contributes to charge and spin properties for various applications, including data and energy storage. Here, a low temperature assisted co-precipitation method produced a series of Co doped ZnO nanoparticles. After structural characterizations, zinc vacancy defects were realized via the hyperfine signal with g ∼ 1.96 (spin resonance) and the emissions (photoluminescence) at 410 and 465 nm. The synergistic effect among the Co dopant, native, and polaron defects makes the system exhibit enhanced polarization and electrochemical reactions. Magnetization hysteresis curves demonstrate the intrinsic magnetic nature of the materials that are essential for realizing useful polaronic states. As an anode material, 20 at. % Co doped electrode has a higher specific capacitance and superior cycling stability with charge retention above 98 %, which is much higher than the other ZnO-based electrodes and is associated with the polaron-assisted rapid redox reactions. These polarons also stimulate a ferroelectric polarization of 0.28 μC cm−2 via local lattice distortion. All these findings confirm that the Co doped semi-magnetic ZnO system with multifunctionality is adequate for employment in device fabrication as a low-cost, highly stable material.

Different polymorphs of Y doped HfO2 epitaxial thin films: Insights into structural, electronic and optical properties

We report the investigation of local structure, electronic and optical properties of different polymorphs of (YO1.5)x(HfO2)1-x (x = 0, 0.05, 0.10, 0.15, and 0.20) epitaxial thin films on YSZ(100) substrate prepared by pulsed laser deposition technique. The X-ray diffraction results confirm that the deposited films are epitaxial and crystal structure changes from monoclinic to orthorhombic to cubic/tetragonal as Y concentration increases in HfO2 thin films. Spectroscopic identification of phase transformation in these thin films was investigated using Fourier transform infrared and X-ray absorption spectroscopy (XAS). Effect of crystal structure on Hf-O & Hf-Hf bond distances and disorder were investigated by extended X-ray absorption fine structure. O K-edge XAS spectra show profound changes in eg and t2g peaks for different HfO2 polymorphs. X-ray photoelectron spectroscopic studies confirm that different chemical environments are present in different polymorphs of HfO2 thin film. The photoluminescence measurements validate the wide band spectral emission in wavelength region of 400–550 nm for all polymorphs and photoluminescence areal intensity shows strong dependence on phase and local structure disorder. This work will be helpful in understanding the basic material properties and spectroscopic identification of different HfO2 phases of high application relevance in semiconductor industry.

Investigation of local structures of silicon oxynitride glasses prepared from aerogels

Investigation of local structures of silicon oxynitride glasses prepared from aerogels

Probing the electronic and local structure of Sr2−xLaxCoNbO6 using near-edge and extended x-ray absorption fine structures

We report the electronic and local structural investigation of double pervoskites Sr$_{2-x}$La$_x$CoNbO$_6$ ($x=$ 0--1) using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structures (EXAFS) at the Nb, Co, and Sr $K$-edges. The $ab$ $initio$ simulations and detailed analysis of the Nb and Co $K$-edge XANES spectra demonstrate that the observed pre-edge features arise from the transition of 1$s$ electrons to the mixed $p-d$ hybridized states. We reveal a $z$-out Jahn-Teller (JT) distortion in the CoO$_6$ octahedra, which decreases monotonically due to an enhancement in the JT inactive Co$^{2+}$ ions with $x$ . On the other hand, the $z$-in distortion in NbO$_6$ octahedra remains unaltered up to $x=$ 0.4 and then decreases with further increase in $x$. This sudden change in the local coordination around Nb atoms is found to be responsible for the evolution of the antiferromagnetic interactions in $x \geqslant$ 0.6 samples. Also, we establish a correlation between the degree of octahedral distortion and intensity of the white line feature in the XANES spectra and possible reason for this are discussed. More interestingly, we observe the signature of KN$_1$ double electron excitation in the Sr $K$-edge EXAFS spectra for all the samples, which is found to be in good agreement with the $Z$+1 approximation. Further, the Co L$_{2,3}$ edge shows the reduction in the crystal field strength and hence an increase in the charge transfer energy ($\Delta_{ct}$) with the La substitution.