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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

3D Lead-Organoselenide-Halide Perovskites and their Mixed-Chalcogenide and Mixed-Halide Alloys

Here, we incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS ( + NH 3 (CH 2 ) 2 Se - ), which occupies both the X - and A + sites in the prototypical ABX 3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX 2 (X=Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77 Se and 207 Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX 2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable band gap decrease. Optical absorbance measurements indeed show band gaps of 2.07 and 1.86 eV for (SeCYS)PbX 2 with X=Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the band gap from 1.86 to 2.31 eV–straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the band gap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO 3 Nanocubes

Here, surface adsorbates and surrounding matrix species have been demonstrated to affect the properties of nanoscale ferroelectrics and nanoscale ferroelectric composites; potentially counteracting performance losses that can occur in small particle sizes. In this work, the effects of nonpolar oleic acid (OA) and polar tetrafluoroborate (BF 4 - ) ligand capping on the surface of various sizes of BaTiO 3 nanocubes have been investigated with combined neutron diffraction and neutron pair distribution function (PDF), density functional theory (DFT), and ab initio molecular dynamics (AIMD) methods. The low real space PDF region provides an unobstructed view of rhombohedral (split short and long) Ti-O distances in BaTiO 3 nanocubes, mimicking the well-established order-disorder local structure found in bulk BaTiO 3 . Interestingly, the intermediate-range order in nanocubes is found to be orthorhombic, rather than tetragonal. It is concluded that polar ligands adsorbed at BaTiO 3 surfaces stabilize the correlation length scale of local rhombohedral distortions in ferroelectric nanoparticles relative to nonpolar ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Probing of Local Structure in Laves Compound TbFe 2

Abstract The Laves compounds Tb 1‐x Dy x Fe 2 have attracted much interest due to the giant magnetostriction effect appearing at their morphotropic phase boundary compositions. Although previous studies have established the relationship between the average structure and magnetostrictive properties in these compounds, there is a lack of characterization of their local structures. In this paper, as a first step toward this goal, the evolution of the local structure of the terminal compound (TbFe 2 ) of this system is reported, in an attempt to provide useful information about interatomic bonding in this system. The pair distribution function (PDF) results suggest that the compound presents the rhombohedral local crystal symmetry. The lattice at the local scale shows abnormal thermal expansion which is different from the long scale structure. The different role of the Tb─Fe bond and Fe─Fe bond in affecting the crystal lattice is revealed. These findings highlight the important role of local structure in determining the magnetostrictive properties of the Laves compounds.

Kou, Ronghui↗
DOE OSTI2024

Mo 3 S 13 Chalcogel: A High-Capacity Electrode for Conversion-Based Li-Ion Batteries

Despite large theoretical energy densities, metal-sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution-processable, room temperature (RT) synthesis, local structures, and application of a sulfur-rich Mo 3 S 13 chalcogel as a conversion-based electrode for lithium-sulfide batteries (LiSBs). The structure of the amorphous Mo 3 S 13 chalcogel is derived through operando Raman spectroscopy, synchrotron X-ray pair distribution function (PDF), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three-dimensional (3D) network is the connection of Mo 3 S 13 units through S–S bonds. Li/Mo 3 S 13 half-cells deliver initial capacity of 1013 mAh g –1 during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g –1 at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high-capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo–S coordination in Mo 3 S 13 chalcogel. Importantly, these findings showcase the potential of Mo 3 S 13 chalcogels as metal-sulfide electrode materials for LiSBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Structural Properties of Nanometer‐Sized Gold Nanoparticles on a Silicon Substrate

Properties of gold nanoparticles (Au NPs) supported on Si substrates, which have been the focus of recent attention, depend sensitively on the size, structure, and coordination of Au NPs as well as on the processes of interdiffusion and chemical bonding at the Au–Si interface. There is a great need, therefore, for developing structural techniques capable of imaging such nanosystems in atomic detail. Here, it is discussed how the atomic structure of nanometer‐sized Au NPs deposited on a silicon surface can be determined by using high‐energy X‐ray diffraction measurements in combination with an analysis based on atomic‐pair‐distribution functions and advanced reverse Monte Carlo methods. This approach delivers simple and incisive pictures of the structure of Au clusters on Si and reveals direct structural evidence for the emergence of a Au‐silicide interface following room temperature deposition of Au NPs on Si. This study will contribute to designing Au/Si nanostructures with desirable properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Tailored (La 0.2 Pr 0.2 Nd 0.2 Tb 0.2 Dy 0.2 ) 2 Ce 2 O 7 as a Highly Active and Stable Nanocatalyst for the Oxygen Evolution Reaction

Abstract Designing highly active and robust catalysts for the oxygen evolution reaction is key to improving the overall efficiency of the water splitting reaction. It has been previously demonstrated that evaporation induced self‐assembly (EISA) can be used to synthesize highly porous and high surface area cerate‐based fluorite nanocatalysts, and that substitution of Ce with 50% rare earth (RE) cations significantly improves electrocatalyst activity. Herein, the defect structure of the best performing nanocatalyst in the series are further explored, Nd 2 Ce 2 O 7 , with a combination of neutron diffraction and neutron pair distribution function analysis. It is found that Nd 3 + cation substitution for Ce in the CeO 2 fluorite lattice introduces higher levels of oxygen Frenkel defects and induces a partially reduced RE 1.5 Ce 1.5 O 5 +x phase with oxygen vacancy ordering. Significantly, it is demonstrated that the concentration of oxygen Frenkel defects and improved electrocatalytic activity can be further enhanced by increasing the compositional complexity (number of RE cations involved) in the substitution. The resulting novel compositionally‐complex fluorite– (La 0.2 Pr 0.2 Nd 0.2 Tb 0.2 Dy 0.2 ) 2 Ce 2 O 7 is shown to display a low OER overpotential of 210 mV at a current density of 10 mAcm −2 in 1M KOH, and excellent cycling stability. It is suggested that increasing the compositional complexity of fluorite nanocatalysts expands the ability to tailor catalyst design.

Chemistry↗
DOE OSTI2024

Amorphous K–Co–Mo–S x Chalcogel: A Synergy of Surface Sorption and Ion-Exchange

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. We report the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K 2 CoMo 2 S 10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo 5+ 2 and Mo 4+ 3 clusters in the vicinity of di/polysulfides which are covalently linked by Co 2+ ions. The ionically bound K + ions remain in the percolating pores of the Co–Mo–S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO 2 2+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO 2 2+ ] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Central Role of Oxo Clusters in Zirconium‐Based Esterification Catalysis

Oxo clusters are a unique link between oxide nanocrystals and Metal‐Organic Frameworks (MOFs), representing the limit of downscaling each of the respective crystals. Herein, the superior catalytic activity of clusters, compared to zirconium MOF UiO‐66 and nanocrystals is shown. Focus is on esterification reactions given their general importance in consumer products and the challenge of converting large substrates. Oxo clusters have a higher surface‐to‐volume ratio than nanocrystals, rendering them more active. For large substrates, for example, oleic acid, MOF UiO‐66 has negligible catalytic activity while clusters provide almost quantitative conversion, a fact we ascribe to limited diffusion of large substrates through the MOF pores. Clusters do not suffer from limited mass transfer and we also obtain high conversion in solvent‐free reactions with sterically hindered alcohols (hexanol, 2‐ethyl hexanol, benzyl alcohol, and neopentyl alcohol). The cluster catalyst can be recovered and shows identical activity when reused. The structural integrity of the cluster is confirmed using X‐ray total scattering and pair distribution function analysis. Moreover, when homogeneous zirconium alkoxides are used as catalysts, the same oxo cluster is retrieved, showing that oxo clusters are the active catalytic species, even in previously assumed homogeneously catalyzed reactions.

Pulparayil Mathew, Jikson↗
DOE OSTI2025

Electron Microscopy Approaches to Unraveling the Structure of Amorphous Materials

Determining atomic structures in crystalline materials—where atoms are arranged in rigid, periodic lattices—has been highly successful using probes such as electrons, X-rays, and neutrons. In contrast, amorphous materials, despite their ubiquity and technological importance, remain far more challenging to characterize with comparable accuracy and precision. This review highlights existing, emerging, and potential (scanning) transmission electron microscopy ((S)TEM) techniques for probing short- and medium-range order in amorphous materials. Approaches ranging from high-resolution (S)TEM imaging and selected electron diffraction pattern to four-dimensional STEM (4D-STEM) based pair distribution function, fluctuation electron microscopy, tomography, ptychography, and spectroscopic methods are discussed, emphasizing their ability to provide complementary insights across multiple length scales—from sub-angstrom local environments to nanometer-scale correlations. Here, we further explore the promise of multimodal and correlative strategies, as well as the growing role of machine learning and physics-informed AI in enabling real-time, quantitative interpretation of complex structural signatures. Together, these advances point toward a future where electron microscopy not only reveals the hidden order in amorphous systems but also establishes robust structure–property relationships, paving the way for materials innovation in disordered matter.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Deformation-enhanced hierarchical multiscale structure heterogeneity in a Pd-Si bulk metallic glass

Here, the multiscale structures in a Pd 82 Si 18 binary bulk metallic glass before and after deformation were studied using electron microscopies, high-energy synchrotron X-ray diffraction, and small-angle scattering techniques. The experimental results revealed an enhancement of hierarchical structure heterogeneities on multiple length scales after deformation. Hierarchical multiple shear bands of high number density were observed after bending, introducing complex but periodically distributed residual strain. Pair distribution function analysis revealed that the connectivity of the short-range clusters on the medium-range scale determines the packing density difference between the tension side and the compression side in the sample after bending. In-situ synchrotron X-ray diffraction study also revealed a transformation of connection modes among short-range clusters under uniaxial tension and compression, which is consistent with those of triaxial tension/compression parts upon bending in Pd 82 Si 18 glassy alloys. The nanoscale heterogeneities for metallic glasses after deformation observed by small-angle scattering and transmission electron microscopy may be attributed to the nanoscale amorphous phase separation and interacting multiple shear bands enhanced by plastic deformation. Our findings suggested that the enhancement of hierarchical heterogeneous structure on multiple length scales may explain the excellent plasticity of Pd-Si glassy alloys, deepening the understanding of structure-property relation during plastic deformation in metallic glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Structural and thermodynamic evolution of an amorphous SiOC ceramic after swift heavy ion irradiation

Radiation induced structural and energetic changes have been widely studied in crystalline materials, but studied to a much lesser extent in amorphous solids. Using a combination of neutron pair distribution function (PDF) analysis and high temperature oxide melt solution calorimetry, we obtained critical insights into the structural and energetic evolution in a swift heavy ion irradiated amorphous SiOC polymer-derived ceramic. The radiation modified SiOC structure becomes energetically less stable by 24.0±1.6 kJ/mol compared to the unirradiated structure. This destabilization is related to decreased connectivity of the Si-O-C network and destruction of free carbon. In comparison with unirradiated SiOC, the irradiated structure is more likely to become phase separated during subsequent thermal annealing. Here, our study has important implications for evaluating amorphous SiOC ceramic as a possible radiation resistant structure for nuclear applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Correlating hidden local structural distortion with antiferroelectric-ferroelectric transition in PbZrO 3 -based perovskites

Externally stimulated antiferroelectric-ferroelectric (AFE-FE) transition makes AFE materials attractive for many applications ranging from energy storage to sensing. This transition-mediated macroscopic electrical characteristics have been extensively investigated, yet the underlying structural evolution remains poorly understood. Herein, we study the local- and long-range structural evolutions in the Nb-doped Pb(Zr,Sn,Ti)O 3 perovskites by in-situ X-ray total scattering and diffraction, which show three different types of AFE-FE transitions. The evolution of long-range structure from diffraction and local structure identified by atomic pair distribution function (PDF) are consistent well with the phase transition behavior indicated by macroscopic polarization/strain measurements, while discrepancies exist. Interestingly, frequently employed long-range structure picture that the uniform AFE pseudo-tetragonal to FE rhombohedral transformation is insufficient to understand the distinct composition-dependent AFE-FE transition behaviours. Instead, the reversibility of this transition correlates with the chemically sensitive local atomic displacements revealed by newly developed in-situ PDF. The critical electric field of transition is associated with the local structural differences between the AFE and FE state. The macroscopic electrostrains can be well estimated by the phase transition associated lattice strain and domain alignment from in-situ synchrotron XRD data, while the local strains calculated from in-situ PDFs are found to be much lower. Finally, these results provide a fresh insight into the AFE-FE transition, and advance the understanding of structure-property relationships in AFE materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Multi-scale structural analysis of swift heavy ion-irradiated ZrO 2 and HfO 2

The radiation-induced monoclinic-to-tetragonal phase transition in ZrO 2 and HfO 2 has been the subject of many investigations, but the transformation pathways and underlying structural mechanisms are still not well understood. In this study, microcrystalline powder samples of ZrO 2 and HfO 2 were irradiated with 946 MeV and 1470 MeV Au ions to a wide fluence range up to 3 × 10 13 ions/cm 2 . To characterize beam-induced structural modifications across all spatial length scales, complementary experimental techniques such as synchrotron X-ray diffraction and spallation neutron total scattering were used. The phase evolution of the tetragonal polymorph with increasing ion fluence is accurately described by a heterogeneous track-overlap model that incorporates both direct- and double-impact processes. These damage accumulation processes are an expression of a core-shell ion track morphology that depends on irradiation conditions and target material. Neutron pair distribution function analysis revealed that ion-beam-induced tetragonal ZrO 2 is merely a configurational average of short-range orthorhombic (Pbcn) domains stabilized by a dense network of domain walls. Furthermore, this knowledge is critical for a better understanding of how crystalline-to-crystalline phase transformations proceed at the atomic scale under extreme conditions.

Monoclinic-to-tetragonal phase transformation↗
DOE OSTI2025

Roles of surface Mn(III) and MgOH + /CaOH + complexation in photochemically assisted Mn 2+ oxidation and Todorokite formation

Todorokite, a Mn oxide phase commonly found in seafloor Mn nodules, is one of the most abundant Mn oxides in nature and has wide applications in environmental engineering, including heavy metal remediation, contaminant adsorption for water purification, and catalysis for organic pollutant degradation. However, traditional abiotic formation of todorokite reported to date typically requires high temperature, pressure, and pH outside circumneutral conditions, or involves several days of phase transformations from precursor phases. In this study, we demonstrate rapid todorokite formation within 6 h via photochemically assisted oxidation of Mn 2+ (aq) in the presence of Mg 2+ or Ca 2+ , notably at ambient temperature and pressure. The concentrations of aqueous MgOH + and CaOH + , as well as the pH (initial 9 or 6), had significant collective influences on the crystalline phases of the formed Mn oxide solids. The proportions of the Mn oxidation states (IV, III, and II) and the extent of Mn(III) surface complexation with MgOH + or CaOH + controlled the crystalline phases (todorokite, feitknechtite, and birnessite) and the extent of cation incorporation into the resulting Mn oxide solids. Specifically, the oxidation state of Mn influenced the crystallization of different Mn oxide phases, and the formed Mn(III) complexed with MgOH + or CaOH + facilitated the formation of todorokite, along with cation incorporation. X-ray pair distribution function analysis revealed that incorporated Mg species were located at the inside corner sites of the 5 × 3 MnO 6 octahedral tunnel structure of todorokite, suggesting complexation between MgOH + and Mn(III) at the corners of the tunnel. Furthermore, this study provides novel insights into the elusive formation of todorokite and its potential for applications in advanced water treatment and environmental remediation.

Abiotic Mn2+ oxidation↗
DOE OSTI2021

Local structure and Ca/Si ratio in C-S-H gels from hydration of blends of tricalcium silicate and silica fume

At the microscale, C-S-H gels from alite, or neat Portland cements, has a Ca/Si ratio close to 1.80. At the nanoscale, C-S-H is described by a defective tobermorite structure which allows a maximum Ca/Si ratio close to 1.40. There is no agreement in the location of the extra 0.40 mol of Ca(OH){sub 2} at the nanoscale. Atomistic modelling studies reported Ca(OH){sub 2} species within the tobermorite interlayer space. Other works point toward a fine intermixing of defective tobermorite and nanoportlandite. Here, we have prepared a series of alite blended with silica fume and studied the pastes by several techniques including synchrotron pair distribution function (PDF). In the employed conditions, the C-S-H gel formed by the pozzolanic reaction has nearly the same local structure than the primary C-S-H gel. Furthermore, differential PDF points toward Ca(OH){sub 2} excess having a local structure compatible with few-layer thick nanoparticles stretched along the c-axis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Energetics of hydroxylbastnäsite solid solutions, La 1-$\chi$ Nd $\chi$ CO 3 OH

Bastnäsites (LnCO 3 (F,OH)) are a group of common rare earth elements (REE)-bearing minerals and are one of the primary global sources of REE. Due to the chemical similarities among REE, bastnӓsites tend to occur as solid solutions instead of end members in REE containing ores. To better understand the processes and the mechanisms of formation of such deposits, it is essential to determine the thermodynamic properties of bastnӓsites, including hydroxylbastnӓsite (LnCO 3 OH) solid solutions. In this work, we performed detailed structural and calorimetric investigations on synthetic hexagonal La–Nd hydroxylbastnӓsite (La 1-$\chi$ NdCO 3 OH, $\chi$ = 0, 0.25, 0.5, 0.75, 1) solid solutions. X-ray diffraction confirms the crystal structure of the solid solution series in the $\ P$6 space group, and pair distribution function (PDF) analysis reveals local bonding environments characterized by three different types of 9-coordinated metal-oxygen polyhedra. Unit cell parameters of La1–xNdxCO3OH exhibit a nearly linear relation with the Nd content x, suggesting a random distribution of La and Nd in the structure. Their standard enthalpies of formation (Δ$\ H$° f ) were determined by high temperature oxide melt drop solution calorimetry, from which the enthalpies of mixing (Δ$\ H$ mix ) were derived. The Δ$\ H$ mix can be fitted by a regular solution model with an interaction parameter of 12.58 ± 0.16 kJ/mol, suggesting enthalpic metastability of La1–xNdxCO3OH relative to the two endmembers. Combining entropy and enthalpy, we further estimated the Gibbs free energies of mixing (Δ$\ G$ mix ) at relevant temperatures, revealing favorable temperatures under which the intermediate La 1-$\chi$ NdCO 3 OH phases can be stabilized. Such entropy-driven stabilization, as is consistent with our geochemical modeling results, may explain the enhancement of thermal stability of the solid solutions in nature. Additionally, the temperature range constrained from this study may be used to estimate the thermal history of REE bastnӓsite deposit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hot-melt extrudability of amorphous solid dispersions of flubendazole-copovidone: An exploratory study of the effect of drug loading and the balance of adjuvants on extrudability and dissolution

The FDA-approved anthelmintic flubendazole has shown potential to be repositioned to treat cancer and dry macular degeneration; however, its poor water solubility limits its use. Amorphous solid dispersions may overcome this challenge, but the balance of excipients may impact the preparation method and drug release. Here, we evaluate the influence of adjuvants and drug loading on the development of an amorphous solid dispersion of flubendazole-copovidone by hot-melt extrusion. The drug, copovidone, and adjuvants (magnesium stearate and hydroxypropyl cellulose) mixtures were statistically designed, and the process was performed in a twin-screw extruder. The study showed that flubendazole and copovidone mixtures were highly extrudable, except when drug loading was high (>40%). Furthermore, magnesium stearate positively impacted the extrusion and was more effective than hydroxypropyl cellulose. The extruded materials were evaluated by modulated differential scanning calorimetry and X-ray powder diffraction, obtaining positive amorphization and physical stability results. Pair distribution function analysis indicated the presence of drug rich domains with medium-range order structure and no evidence of polymer-drug interaction. All extrudates presented faster dissolution (HCl, pH 1.2) than pure flubendazole, and both adjuvants had a notable influence on the dissolution rate. In conclusion, hot-melt extrusion may be a viable option to obtain stable flubendazole: copovidone amorphous dispersions.

60 APPLIED LIFE SCIENCES↗