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At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Long- and Short-Range Constraints for the Structure Determination of Layered Silicates with Stacking Disorder

Layered silicates have important applications as host materials, supports for catalysis, and zeolite precursors. However, their local structures are often challenging to establish due to disorder of the sheet assemblies. We present a new protocol that combines long- and short-range structural constraints from diffraction and solid-state NMR techniques, respectively, to determine the molecular structure of layered silicates in the presence of various extents of stacking disorder. Solid-state 29Si NMR data are largely insensitive to the incomplete extent of three-dimensional (3D) crystallinity that limits the interpretation of diffraction data alone to the identification of possible unit cells and space groups. State-of-the-art NMR crystallography techniques consequently provide a simplified view of materials from which candidate framework structures can be built and evaluated based on local structural constraints, including interatomic distances, Si site numbers and multiplicities, and Si–O–Si connectivities, and refined using density functional theory. This protocol was applied to a new layered silicate material named CLS-1, of composition [Si5O11H][C9N2H15]·1.9(H2O), synthesized by using a fluoride-based protocol and cationic alkylaminopyridinium as a structure-directing agent (SDA). Despite the intrinsic complexity and partial ordering of the intersheet arrangements and organic–inorganic interactions, this led to the identification of a single space group that is compatible with both NMR and diffraction data, from which the silicate framework structure could be established,. The remarkable similarities between the layered framework structures of CLS-1, HUS-2 (Tsunoji et al. J. Mater. Chem.2012, 22, 13682), and another layered silicate material with a radically different morphology and extent of stacking order and interlayer dynamics, established by using a similar approach (Brouwer et al. J. Am. Chem. Soc.2013, 135, 5641), point to the remarkable robustness of this previously unknown silicate framework type.

Cadars, Sylvian↗
DOE OSTI2013

Electron density distribution and crystal structure of 27R-AlON, Al{sub 9}O{sub 3}N{sub 7}

The crystal structure of Al{sub 9}O{sub 3}N{sub 7} was characterized by laboratory X-ray powder diffraction (CuKα{sub 1}). The title compound is trigonal with space group R3-bar m (centrosymmetric). The hexagonal unit-cell dimensions (Z=3) are a=0.30656(2) nm, c=7.2008(3) nm and V=0.58605(5) nm{sup 3}. The initial structural model was derived by the powder charge-flipping method and subsequently refined by the Rietveld method. The final structural model showed the positional disordering of two of the five types of Al sites. The maximum-entropy method-based pattern fitting method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The disordered crystal structure was successfully described by overlapping five types of domains with ordered atom arrangements. The distribution of atomic positions in one of the five types of domains can be achieved in the space group R3{sup ¯}m. The atom arrangements in the four other domains are noncentrosymmetric with the space group R3m. Two of the four types of domains are related by a pseudo-symmetry inversion, and the two remaining domains also have each other the inversion pseudo-symmetry. The very similar domain structure has been also reported for 21R-AlON (Al{sub 7}O{sub 3}N{sub 5}) in our previous study. - Graphical abstract: A bird’s eye view of electron densities up to 50% (0.074 nm{sup −3}) of the maximum on the plane parallel to (110) with the corresponding atomic arrangements of Al{sub 9}O{sub 3}N{sub 7}. Highlights: • Crystal structure of Al{sub 9}O{sub 3}N{sub 7} is determined by laboratory X-ray powder diffraction. • The atom arrangements are represented by the split-atom model. • The maximum-entropy method-based pattern fitting method is used to confirm the validity of the model. • The disordered structure is described by overlapping five types of domains with ordered atom arrangements.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Crystal structure of HgGa{sub 2}Se{sub 4} under compression

Highlights: ► Single crystals of HgGa{sub 2}Se{sub 4} with defect-chalcopyrite structure were synthesized. ► HgGa{sub 2}Se{sub 4} exhibits a phase transition to a disordered rock salt structure at 17 GPa. ► HgGa{sub 2}Se{sub 4} undergoes a phase transition below 2.1 GPa to a disordered zinc blende. - Abstract: We report on high-pressure x-ray diffraction measurements up to 17.2 GPa in mercury digallium selenide (HgGa{sub 2}Se{sub 4}). The equation of state and the axial compressibilities for the low-pressure tetragonal phase have been determined and compared to related compounds. HgGa{sub 2}Se{sub 4} exhibits a phase transition on upstroke toward a disordered rock-salt structure beyond 17 GPa, while on downstroke it undergoes a phase transition below 2.1 GPa to a phase that could be assigned to a metastable zinc-blende structure with a total cation-vacancy disorder. Thermal annealing at low- and high-pressure shows that kinetics plays an important role on pressure-driven transitions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dispersion and Mixing in Three-Dimensional Discrete Fracture Networks: Nonlinear Interplay Between Structural and Hydraulic Heterogeneity: DISPERSION AND MIXING-REGULAR VERSUS DISORDERED NETWORKS

We investigate the relative impact of topological, geometric, and hydraulic heterogeneity on transport processes in three-dimensional fracture networks. Focusing on the two largest scales of heterogeneity in these systems, individual fracture and network structure, we compare transport through analogous structured and disordered three-dimensional fracture networks with varying degrees of hydraulic heterogeneity. For the moderate levels of hydraulic heterogeneity we consider, network structure is the dominant control of transport through the networks. Less dispersion, both longitudinal and transverse, is observed in structured networks than in disordered networks, due in part to the higher connectivity in the former, independent of the level of hydraulic heterogeneity. However, increases in dispersion with higher hydraulic heterogeneity are larger in the disordered networks than in the structured networks, thereby indicating that the interplay between structural and hydraulic heterogeneity is nonlinear. Here, we propose a measure of disorder in fracture networks by computing the Shannon entropy of the spectrum of the Laplacian of a weighted graph representation of the networks, where the weights are given by a combination of topological, geometric, and hydraulic properties. Finally, this metric, as a relative indicator by comparison between two networks, is a first approach to the dispersion potential and “mixing capacity” of a fracture network.

58 GEOSCIENCES↗
DOE OSTI2021

High temperature transition aluminas in gamma-Al2O3: Review

High temperature treated transition aluminas display adsorptive and catalytic properties that are in many ways comparable to those of their low temperature counterpart gamma-Al2O3. While being important industrial catalysts as well as catalytic supports, their very basic crystallographic and structural characteristics remain poorly understood and thus actively studied. In this review, we critically examine the crystallography and structural complexity of these materials. Specifically, we address the crystallography of delta- and theta-Al2O3 polymorphs and show how structural intergrowth and disorder are accommodated in these phases. The structural complexity at the scale of overall microstructure is also examined, and the challenges and recent progress in quantification of the structure at ensemble level are discussed. Most pertinently to catalysis, we review the surfaces properties of high temperature treated Al2O3 and discuss the implications for understanding attributes relevant to heterogeneous catalysis.

Kovarik, Libor↗
DOE OSTI2025

Entropy-Driven Structural Evolution in Ceramic Oxides

High-entropy ceramics, with five or more elements randomly occupying the same cation crystallographic sites, offer vast compositional diversity and unique properties for material design and applications. However, for many dissimilar elements, entropic stabilization cannot overcome the enthalpic barrier to cation substitution. As a result, most high-entropy ceramics incorporate only a few similar elements, limiting the in-depth exploration of the effect of entropy on ceramic properties. Here, we first use density functional theory to model fluorite crystal structures composed of 1-10 elements and then experimentally present practical fluorite oxide nanostructures containing 1, 3, 8, and 15 metals, as well as a record-breaking 25-element high-entropy ceramic incorporating a diverse palette of rare-earth, transition, alkaline, p-block, and noble metals. As entropy increases, structural and configurational disorder in the solid solution rises, altering structural features such as lattice distortion, crystallinity, homogeneity, defect density, and thermal stability. This research provides new insights and understanding of the role of entropy in stabilizing compositionally complex ceramics.

Liu, Shuo↗
DOE OSTI2014

The structure of CO{sub 2} hydrate between 0.7 and 1.0 GPa

A deuterated sample of CO{sub 2} structure I (sI) clathrate hydrate (CO{sub 2}·8.3 D{sub 2}O) has been formed and neutron diffraction experiments up to 1.0 GPa at 240 K were performed. The sI CO{sub 2} hydrate transformed at 0.7 GPa into the high pressure phase that had been observed previously by Hirai et al. [J. Phys. Chem. 133, 124511 (2010)] and Bollengier et al. [Geochim. Cosmochim. Acta 119, 322 (2013)], but which had not been structurally identified. The current neutron diffraction data were successfully fitted to a filled ice structure with CO{sub 2} molecules filling the water channels. This CO{sub 2}+water system has also been investigated using classical molecular dynamics and density functional ab initio methods to provide additional characterization of the high pressure structure. Both models indicate the water network adapts a MH-III “like” filled ice structure with considerable disorder of the orientations of the CO{sub 2} molecule. Furthermore, the disorder appears to be a direct result of the level of proton disorder in the water network. In contrast to the conclusions of Bollengier et al., our neutron diffraction data show that the filled ice phase can be recovered to ambient pressure (0.1 MPa) at 96 K, and recrystallization to sI hydrate occurs upon subsequent heating to 150 K, possibly by first forming low density amorphous ice. Unlike other clathrate hydrate systems, which transform from the sI or sII structure to the hexagonal structure (sH) then to the filled ice structure, CO{sub 2} hydrate transforms directly from the sI form to the filled ice structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Phonon and magnetic structure in δ-plutonium from density-functional theory

We present phonon properties of plutonium metal obtained from a combination of density-functional-theory (DFT) electronic structure and the recently developed compressive sensing lattice dynamics (CSLD). The CSLD model is here trained on DFT total energies of several hundreds of quasi-random atomic configurations for best possible accuracy of the phonon properties. The calculated phonon dispersions compare better with experiment than earlier results obtained from dynamical mean-field theory. The density-functional model of the electronic structure consists of disordered magnetic moments with all relativistic effects and explicit orbital-orbital correlations. The magnetic disorder is approximated in two ways: (i) a special quasi-random structure and (ii) the disordered-local-moment (DLM) method within the coherent potential approximation. Magnetism in plutonium has been debated intensely, However, the present magnetic approach for plutonium is validated by the close agreement between the predicted magnetic form factor and that of recent neutron-scattering experiments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Mechanistic insight of KBiQ 2 (Q = S, Se) using panoramic synthesis towards synthesis-by-design

Solid-state synthesis has historically focused on reactants and end products; however, knowledge of reaction pathways, intermediate phases and their formation may provide mechanistic insight of solid-state reactions. With an increased understanding of reaction progressions, design principles can be deduced, affording more predictive power in materials synthesis. In pursuit of this goal, in situ powder X-ray diffraction is employed to observe crystalline phase evolution over the course of the reaction, thereby constructing a “panoramic” view of the reaction from beginning to end. We conducted in situ diffraction studies in the K–Bi–Q (Q = S, Se) system to understand the formation of phases occurring in this system in the course of their reactions. Powder mixtures of K 2 Q to Bi 2 Q 3 in 1:1 and 1.5:1 ratios were heated to 800 °C or 650 °C, while simultaneously collecting diffraction data. Three new phases, K 3 BiS 3 , β-KBiS 2 , and β-KBiSe 2 , were discovered. Panoramic synthesis showed that K 3 BiQ 3 serves an important mechanistic role as a structural intermediate in both chalcogen systems (Q = S, Se) in the path to form the KBiQ 2 structure. Thermal analysis and calculations at the density functional theory (DFT) level show that the cation-ordered β-KBiQ 2 polymorphs are the thermodynamically stable phase in this compositional space, while Pair Distribution Function (PDF) analysis shows that all α-KBiQ 2 structures have local disorder due to stereochemically active lone pair expression of the bismuth atoms. The formation of the β-KBiQ 2 structures, both of which crystallize in the α-NaFeO 2 structure type, show a boundary where the structure can be disordered or ordered with regards to the alkali metal and bismuth. A cation radius tolerance for six-coordinate cation site sharing of ($\frac{r^+}{r^{3+}}$) ~ 1.3 is proposed. The mechanistic insight the panoramic synthesis technique provides in the K–Bi–Q system is progress towards the overarching goal of synthesis-by-design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Improved synthesis and characterization of the copper Lyonsite-type compound Cu{sub 4−x}Mo{sub 3}O{sub 12}

A novel method involving a molten Ga flux for the synthesis of diffraction quality crystals of the compound Cu{sub 3.82(1)}Mo{sub 3}O{sub 12}, a copper molybdate in the Lyonsite (α-Cu{sub 3}Fe{sub 4}(VO{sub 4}){sub 6}) family, has been developed. Single-crystal X-ray diffraction data have been collected. Cu{sub 3.82(1)}Mo{sub 3}O{sub 12} crystallizes in the space group P2{sub 1}2{sub 1}2{sub 1} with cell dimensions of a=4.9972(1) Å, b=11.0259(3) Å, and c=17.4912(5) Å. Refinement of the resulting structure has enabled modeling of disorder in the channels of the structure and has indicated the localization of copper vacancies to these channel positions. Thermopower measurements indicate that Cu{sub 3.82(1)}Mo{sub 3}O{sub 12} is a rare and interesting example of a cation-deficient n-type material. - Graphical abstract: The unit cell of Cu{sub 3.82(1)}(MoO{sub 4}){sub 3} with displacement ellipsoids drawn at the 75% probability level. Cu is green, Mo is blue, O is red. Highlights: ► A repeatable method for the synthesis Cu{sub 3.82(1)}Mo{sub 3}O{sub 12} has been developed. ► Single crystals were formed from a polycrystalline sample through the use of a gallium flux. ► Thermopower measurements of Cu{sub 3.82(1)}Mo{sub 3}O{sub 12} show n-type behavior.

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

Amorphization mechanism of SrIrO 3 electrocatalyst: How oxygen redox initiates ionic diffusion and structural reorganization

The use of renewable electricity to prepare materials and fuels from abundant molecules offers a tantalizing opportunity to address concerns over energy and materials sustainability. The oxygen evolution reaction (OER) is integral to nearly all material and fuel electrosyntheses. However, very little is known about the structural evolution of the OER electrocatalyst, especially the amorphous layer that forms from the crystalline structure. Here, we investigate the interfacial transformation of the SrIrO 3 OER electrocatalyst. The SrIrO 3 amorphization is initiated by the lattice oxygen redox, a step that allows Sr 2+ to diffuse and O 2− to reorganize the SrIrO 3 structure. This activation turns SrIrO 3 into a highly disordered Ir octahedral network with Ir square-planar motif. The final Sr y IrO x exhibits a greater degree of disorder than IrO x made from other processing methods. Our results demonstrate that the structural reorganization facilitated by coupled ionic diffusions is essential to the disordered structure of the SrIrO 3 electrocatalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Structural properties of ultrafine Ba-hexaferrite nanoparticles

Crystal structure of ultrafine Ba-hexaferrite (BaFe{sub 12}O{sub 19}) nanoparticles was studied using X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDXS), X-ray absorption fine structure (XAFS), and Moessbauer spectroscopy (MS), to be compared to the structure of larger nanoparticles and the bulk. The nanoparticles were synthesized with hydrothermal treatment of an appropriate suspension of Ba and Fe hydroxides in the presence of a large excess of OH{sup -}. The ultrafine nanoparticles were formed in a discoid shape, {approx}10 nm wide and only {approx}3 nm thick, comparable to the size of the hexagonal unit cell in the c-direction. The HRTEM image analysis confirmed the hexaferrite structure, whereas EDXS showed the composition matching the BaFe{sub 12}O{sub 19} formula. XAFS and MS analyses showed considerable disorder of the structure, most probably responsible for the low magnetization. - Graphical abstract: Left: HREM image of an ultrafine Ba-hexaferrite nanoparticle (inset: TEM image of the nanoparticles); Right: the experimental HRTEM image is compared with calculated image and corresponding atomic model. Highlights: Black-Right-Pointing-Pointer Crystal structure of ultrafine Ba-hexaferrite (BaFe{sub 12}O{sub 19}) nanoparticles was compared to the structure of the bulk. Black-Right-Pointing-Pointer Thickness the discoid nanoparticles was comparable to the size of the hexagonal unit cell in the c-direction. Black-Right-Pointing-Pointer Considerable disorder of the nanoparticles' structure is most probably responsible for their low magnetization.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Multimetallic nanoparticle catalysts with enhanced electrooxidation

A new structure-control strategy to optimize nanoparticle catalysis is provided. The presence of Au in FePtAu facilitates FePt structure transformation from chemically disordered face centered cubic (fcc) structure to chemically ordered face centered tetragonal (fct) structure, and further promotes formic acid oxidation reaction (FAOR). The fct-FePtAu nanoparticles show high CO poisoning resistance, achieve mass activity as high as about 2810 mA/mg Pt, and retain greater than 90% activity after a 13 hour stability test.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Structural Heterogeneity and Hydrodynamics of an Intrinsically Disordered Protein Condensate

Biology demonstrates precise control over the free-energy landscape through the selective partitioning of biomacromolecules into membraneless organelles, enabling essential functions such as biochemical transformations, signaling cascades, and mechanical reinforcement. Although the function of these condensates depends on their underlying structure and hydrodynamics, molecular-scale information on these systems remains sparse. Here, in this study, neutron scattering is used to probe the organization and dynamics of the intrinsically disordered N-terminal domain of Galectin-3, an extracellular lectin responsible for facilitating liquid–liquid phase separation on the cellular surface, in both dilute and condensed phases. Dilute solutions contain isolated protein chains in equilibrium with mesoscopic clusters, whereas the condensed phase adopts a bicontinuous, microemulsion-like morphology. The dilute phase behavior is quantitatively described by coarse-grained polymer models from soft-matter physics, demonstrating their predictive power for complex biological proteins. At elevated concentrations, the proteins self-assemble akin to block copolymers, microphase separating through the aggregation of hydrophobic domains along the protein contour. The resulting condensate remains fluid-like despite a 25-fold increase in concentration; its internal hydrodynamics slow by only a factor of 3 relative to dilute protein chains. These results provide a molecular-level framework for how disordered proteins achieve both the structural complexity and dynamic fluidity of biomolecular condensates.

Carrick, Brian R. [Massachusetts Inst. of Technolo↗
DOE OSTI2025

Evolution of Structural Order and Magnetic Anisotropy in Yb 0.5 (Co 1– x Fe x ) 3 Ge 3 through Doping of a Kagome Lattice

Kagome materials provide fruitful grounds for exploring the intersection of topology and magnetism. In this article, the single crystal growth of Yb 0.5 (Co 1–x Fe x ) 3 Ge 3 (x = 0.00, 0.25, 0.50, 0.75, and 1.00) is reported. As Fe is substituted into the Co-containing kagome net, the structure transforms from the disordered Y 0.5 Co 3 Ge 3 /CoSn-type hybrid structure to the ordered HfFe 6 Ge 6 -type structure. Diffusive scattering is observed in all doped concentrations that eventually converge to a single reflection in the Fe end member, ultimately doubling the unit cell along the c-axis. Anisotropic magnetic measurements were performed to evaluate how the magnetism of the kagome lattice is influenced by Fe substitution. Magnetic interactions are primarily observed along the c-axis. Additionally, a reorientation of the magnetic easy axis is observed with increasing Fe incorporation, highlighting how the magnetism of this material can be chemically tuned. Resistivity with unusual behavior observed in the doped compositions is also reported. Furthermore, the rationale behind the structural evolution from disordered to ordered is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On the Effects of Aliovalent Substitutions in Thermoelectric Zintl Pnictides. Varied Polyanionic Dimensionality and Complex Structural Transformations–The Case of Sr 3 ZnP 3 vs Sr 3 Al x Zn 1– x P 3

The structures and the transport properties of a novel family of Zintl phosphides and arsenides with the formula AE 3 ZnPn 3 and the solid solutions AE 3 Al x Zn 1–x Pn 3 , AE 3 ZnAs y P 1–y (AE = Sr, Eu; Pn = P, As) are reported. Crystals of nine new phases have been obtained via Pb-flux reactions and used for structural work by means of single-crystal X-ray diffraction methods. The derived orthorhombic structure is without a direct analog, and features unusual structural units, where the Zn atoms are in both distorted tetrahedral and trigonal-planar coordination of pnictogens. Electronic structure calculations reveal moderately wide bandgaps for Sr 3 ZnP 3 and Sr 3 ZnAs 3 , on the order of 0.70 and 0.63 eV, respectively. Electrical transport measurements above room temperature indicate relatively high resistivity values above 500 K (ρ ≈ 4.8 Ω cm and above), but some of the samples exhibit very high Seebeck coefficients, as large as 300 μV/K at 560 K for Sr 3 ZnAs 3 . Aliovalent substitutions in AE 3 ZnPn 3 , achieved by the partial replacement of Zn 2+ with Al 3+ cations promote occupational and positional disorder, which causes structural transformation towards the disordered variant of the Sr 5 Al 2 Sb 6 structure type. Such substitutions also change the dimensionality of the polyanionic sub-lattice in the resulting quaternary AE 3 Al x Zn 1–x Pn 3 phases. Furthermore, preliminary transport property data on the latter reveal nine times lower electrical resistivity (ρ 500 ≈ 0.5 Ω cm) together with a significantly enhanced Seebeck coefficient, αmax ≈ 430 μV/K at 560 K.

36 MATERIALS SCIENCE↗