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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Porosity Dependence of Compression and Lattice Rigidity in Metal–Organic Framework Series

Porous materials, including metal-organic frameworks (MOFs), are known to undergo structural changes when subjected to applied hydrostatic pressures that are both fundamentally interesting and practically relevant. With the rich structural diversity of MOFs, the development of design rules to better understand and enhance the mechanical stability of MOFs is of paramount importance. In this work, the compressibilities of seven MOFs belonging to two topological families (representing the most comprehensive study of this type to date) were evaluated using in situ synchrotron X-ray powder diffraction of samples within a diamond anvil cell. The judicious selection of these materials, representing widely studied classes of MOFs, provides broadly applicable insight into the rigidity and compression of hybrid materials. An analysis of these data reveals that the bulk modulus depends on several structural parameters (e.g., void fraction and linker length). Furthermore, we find that lattice distortions play a major role in the compression of MOFs. As a result, this study is an important step toward developing a predictive model of the structural variables that dictate the compressibility of porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Large Positive Zero-Field Splitting in the Cluster Magnet Ba 3 CeRu 2 O 9

Herein we present the synthesis and magnetic characterization of a polycrystalline sample of the 6H-perovskite Ba 3 CeRu 2 O 9 , which consists of Ru dimers based on face-sharing RuO 6 octahedra. Our low-temperature magnetic susceptibility, magnetization, and neutron powder diffraction results reveal a nonmagnetic singlet ground state for the dimers. Inelastic neutron scattering, infrared spectroscopy, and the magnetic susceptibility over a wide temperature range are best explained by a molecular orbital model with a zero-field splitting parameter D = 85 meV for the S tot = 1 electronic ground-state multiplet. This large value is likely due to strong mixing between this ground-state multiplet and low-lying excited multiplets, arising from a sizable spin molecular orbital coupling combined with an axial distortion of the Ru 2 O 9 units. Although the positive sign for the splitting ensures that Ba 3 CeRu 2 O 9 is not a single molecule magnet, our work suggests that the search for these interesting materials should be extended beyond Ba 3 CeRu 2 O 9 to other molecular magnets based on metal–metal bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains

Over 20 years after the last inorganic ternary B–P compound was reported, Na 2 BP 2 , a new compound containing one-dimensional B–P polyanionic chains has been synthesized. Common high-temperature synthetic methods required for the direct reaction of boron and phosphorus negate the possible formation of metastable or low temperature phases. In this study, oxidative elimination was used to successfully condense 0D BP 2 3– anionic monomers found in a Na 3 BP 2 precursor into unique 1D BP 2 2– chains consisting of five-member B 2 P 3 rings connected by bridging P atoms in the crystal structure of Na 2 BP 2 . In conclusion, the synthesis was guided by in situ X-ray powder diffraction studies, which revealed the metastable nature of the products of oxidative elimination reactions. Na 2 BP 2 is predicted to be an electron balanced semiconductor which was confirmed by UV–vis spectroscopy with the experimentally determined band gap of 1.1 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

New Family of Argyrodite Thioantimonate Lithium Superionic Conductors

We report on a new family of argyrodite lithium superionic conductors, as solid solutions Li 6+x MxSb 1–x S 5 I (M = Si, Ge, Sn), that exhibit superionic conductivity. These represent the first antimony argyrodites to date. Exploration of the series using a combination of single crystal X-ray and synchrotron/neutron powder diffraction, combined with impedance spectroscopy, reveals that an optimal degree of substitution (x), and substituent induces slight S 2– /I – anion site disorder—but more importantly drives Li + cation site disorder. The additional, delocalized Li-ion density is located in new high energy lattice sites that provide intermediate interstitial positions (local minima) for Li + diffusion and activate concerted ion migration, leading to a low activation energy of 0.25 eV. Excellent room temperature ionic conductivity of 14.8 mS·cm –1 is exhibited for cold-pressed pellets—up to 24 mS·cm –1 for sintered pellets—among the highest values reported to date. This enables all-solid-state battery prototypes that exhibit promising properties. Furthermore, even at -78 °C, suitable bulk ionic conductivity of the electrolyte is retained (0.25 mS·cm –1 ). Selected thioantimonate iodides demonstrate good compatibility with Li metal, sustaining over 1000 h of Li stripping/plating at current densities up to 0.6 mA·cm –2 . The significantly enhanced Li ion conduction and lowered activation energy barrier with increasing site disorder reveals an important strategy toward the development of superionic conductors.

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

Methane hydrate formation in confined nanospace can surpass nature

Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. We report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 degrees C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. Furthermore, the formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelastic neutron scattering experiments and synchrotron X-ray powder diffraction. Our findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).

36 MATERIALS SCIENCE↗
DOE OSTI2019

Structure of amyloid-β (20-34) with Alzheimer’s-associated isomerization at Asp23 reveals a distinct protofilament interface

Amyloid-β (Aβ) harbors numerous posttranslational modifications (PTMs) that may affect Alzheimer’s disease (AD) pathogenesis. Here we present the 1.1 Å resolution MicroED structure of an Aβ 20–34 fibril with and without the disease-associated PTM, L-isoaspartate, at position 23 (L-isoAsp23). Both wild-type and L-isoAsp23 protofilaments adopt β-helix-like folds with tightly packed cores, resembling the cores of full-length fibrillar Aβ structures, and both self-associate through two distinct interfaces. One of these is a unique Aβ interface strengthened by the isoaspartyl modification. Powder diffraction patterns suggest a similar structure may be adopted by protofilaments of an analogous segment containing the heritable Iowa mutation, Asp23Asn. Consistent with its early onset phenotype in patients, Asp23Asn accelerates aggregation of Aβ 20–34, as does the L-isoAsp23 modification. These structures suggest that the enhanced amyloidogenicity of the modified Aβ segments may also reduce the concentration required to achieve nucleation and therefore help spur the pathogenesis of AD.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Control of zeolite microenvironment for propene synthesis from methanol

Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

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

Small-pore hydridic frameworks store densely packed hydrogen

Nanoporous materials have attracted great attention for gas storage, but achieving high volumetric storage capacity remains a challenge. Here, by using neutron powder diffraction, volumetric gas adsorption, inelastic neutron scattering and first-principles calculations, we investigate a magnesium borohydride framework that has small pores and a partially negatively charged non-flat interior for hydrogen and nitrogen uptake. Hydrogen and nitrogen occupy distinctly different adsorption sites in the pores, with very different limiting capacities of 2.33 H 2 and 0.66 N 2 per Mg(BH 4 ) 2 . Molecular hydrogen is packed extremely densely, with about twice the density of liquid hydrogen (144 g H 2 per litre of pore volume). We found a penta-dihydrogen cluster where H 2 molecules in one position have rotational freedom, whereas H 2 molecules in another position have a well-defined orientation and a directional interaction with the framework. This study reveals that densely packed hydrogen can be stabilized in small-pore materials at ambient pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery

Conductive metal sulfides are promising multi-functional additives for future lithium-sulfur (Li-S) batteries. These can increase the sulfur cathode’s electrical conductivity to improve the battery’s power capability, as well as contribute to the overall cell-discharge capacity. This multi-functional electrode design showed initial promise; however, complicated interactions at the system level are accompanied by some detrimental side effects. The metal sulfide additives with a chemical conversion as the reaction mechanism, e.g., CuS and FeS 2 , can increase the theoretical capacity of the Li-S system. However, these additives may cause undesired parasitic reactions, such as the dissolution of the additive in the electrolyte. Studying such complex reactions presents a challenge because it requires experimental methods that can track the chemical and structural evolution of the system during an electrochemical process. To address the fundamental mechanisms in these systems, we employed an operando multimodal x-ray characterization approach to study the structural and chemical evolution of the metal sulfide—utilizing powder diffraction and fluorescence imaging to resolve the former and absorption spectroscopy the latter—during lithiation and de-lithiation of a Li-S battery with CuS as the multi-functional cathode additive. The resulting elucidation of the structural and chemical evolution of the system leads to a new description of the reaction mechanism.

25 ENERGY STORAGE↗
DOE OSTI2013

Structure-composition relationships and optical properties in cerium-substituted (Sr,Ba) 3 (Y,La)(BO 3 ) 3 borate phosphors

Relationships between the structure and composition, and their influence on the optical properties, of a family of cerium-substituted borate compounds with formula A 3 RE(BO 3 ) 3 (A = Ba, Sr; RE = Y, La) are studied using a combination of high resolution synchrotron X-ray powder diffraction and photoluminescence. Examination of the coordination environment of the Ce 3+ active site polyhedra coupled with photoluminescence at 77 K reveal three distinct excitation bands corresponding to Ce 3+ located on three distinct crystallographic sites. Comparing the position of these excitation bands with crystal field splitting effects due to changes in polyhedral volumes and distortions suggest an assignment of the three excitation bands. These compounds are efficiently excited by UV light (≈340 nm) with blue emission at a maximum wavelength of 413 nm for Ba 3 Y(BO 3 ) 3 :Ce 3+ ,Na + , 422 nm for Sr 3 Y(BO 3 ) 3 :Ce 3+ ,Na + , and 440 nm for Sr 3 La(BO 3 ) 3 :Ce 3+ ,Na + . The most efficient compound was determined to be Sr3La(BO 3 ) 3 :Ce 3+ ,Na + with a quantum yield of 50%.

Denault, Kristin A.↗
DOE OSTI2015

Nickel(ii) and copper(i,ii)-based metal-organic frameworks incorporating an extended tris-pyrazolate linker

Solvothermal reactions between the tritopic pyrazole-based ligand 1,3,5-tris((1H-pyrazol-4-yl)phenyl)benzene (H 3 BTPP) and nickel(II) perchlorate or copper(II) nitrate afforded two new metal-organic frameworks, Ni 3 (BTPP) 2 ·solvent (Ni-BTPP) and Cu I 4 Cu II 2 (OH) 2 (BTPP) 2 ·solvent (Cu-BTPP). Powder diffraction structure determination methods were employed to determine the crystal and molecular structure of the copper(I,II) derivative: triangular [Cu3N6(μ3-OH)] nodes are connected to six nearby ones by the pyrazolate ligands, thus constructing flat two-dimensional layers that stack to form slit-like one-dimensional channels. Thermogravimetric analyses highlighted both the thermal stability and the permanent porosity of these two materials. Porosity was confirmed by N 2 adsorption at 77 K, yielding Langmuir specific surface areas of 1923(3) m 2 g -1 and 874(8) m 2 g -1 for Ni-BTPP and Cu-BTPP, respectively. Additionally, Ni-BTPP adsorbed 1.73 mmol g -1 (7.6 wt%) of CO 2 at the mild conditions of 298 K and 1 bar.

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

Long-range antiferromagnetic order in malonate-based compounds Na 2 M(H 2 C 3 O 4 ) 2 ·2H 2 O (M = Mn, Fe, Co, Ni)

In this work, the recently discovered metal-malonate compounds of formulae Na 2 M(H 2 C 3 O 4 ) 2 ·2H 2 O with M = Mn, Fe, Co, Ni are investigated for their magnetic properties. While the Cu-based material is a weak ferromagnet, all other members present antiferromagnetic interactions. Neutron powder diffraction experiments reveal the establishment of a long range magnetic order at low temperature in the Pbca Shubnikov magnetic group. The magnetic structures are characterized by antiferromagnetic layers perpendicular to [001]. These layers are stacked antiparallel (M = Fe) or parallel (M = Mn, Ni) in the ( a , c ) plane. Magnetic moments are collinear to b for the former and to c for the latter. The M = Co malonate exhibits a non-collinear magnetic structure intermediate between the two latter, with components along b and c . Density functional theory calculations indicate that the dominant magnetic interaction, J 1 , occurs along a malonate group via a carboxylate and links two transition metals within the same layer, while other interactions (inter- or intra-layer) are much weaker, so that these compounds present the dominant characteristics of 2D-antiferromagnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Novel multiferroic state and ME enhancement by breaking the AFM frustration in LuMn 1-x O 3

This study provides a comprehensive insight into the effects of controlled off-stoichiometry on the structural and multiferroic properties of the hexagonal manganite LuMn 1-x O 3+δ (x = 0.02; δ ~ 0), supported by neutron powder diffraction measurements confirming single phase P6 3 cm symmetry and evidencing a relevant ferromagnetic component, below T N ~ 90 K, which breaks the archetypal geometrically frustrated antiferromagnetic state typically ascribed to LuMnO 3 . Furthermore, the perturbations in the triangular disposition of spins prompt an additional electric polarization contribution and a clear enhancement of the magnetoelectric coupling which are in good agreement with the results of first principles calculations. In addition, Raman spectroscopy, dielectric permittivity, pyroelectric current and magnetic measurements as a function of temperature point out the precursor effects of the magnetic phase transitions involving a strong coupling between spins, lattice and electric order, even above the Néel temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

Here, in this study, novel filled skutterudites Ba y Ni 4 Sb 12-x Sn x (y max = 0.93) have been prepared by arc melting followed by annealing at 250, 350 and 450°C up to 30 days in vacuum-sealed quartz vials. Extension of the homogeneity region, solidus temperatures and structural investigations were performed for the skutterudite phase in the ternary Ni–Sn–Sb and in the quaternary Ba–Ni–Sb–Sn systems. Phase equilibria in the Ni–Sn–Sb system at 450°C were established by means of Electron Probe Microanalysis (EPMA) and X-ray Powder Diffraction (XPD). With rather small cages Ni 4 (Sb,Sn) 12 , the Ba–Ni–Sn–Sb skutterudite system is perfectly suited to study the influence of filler atoms on the phonon thermal conductivity. Single-phase samples with the composition Ni 4 Sb 8.2 Sn 3.8 , Ba 0.42 Ni 4 Sb 8.2 Sn 3.8 and Ba 0.92 Ni 4 Sb 6.7 Sn 5.3 were used to measure their physical properties, i.e. temperature dependent electrical resistivity, Seebeck coefficient and thermal conductivity. The resistivity data demonstrate a crossover from metallic to semiconducting behaviour. The corresponding gap width was extracted from the maxima in the Seebeck coefficient data as a function of temperature. Single crystal X-ray structure analyses at 100, 200 and 300 K revealed the thermal expansion coefficients as well as Einstein and Debye temperatures for Ba 0.73 Ni 4 Sb 8.1 Sn 3.9 and Ba 0.95 Ni 4 Sb 6.1 Sn 5.9 . These data were in accordance with the Debye temperatures obtained from the specific heat (4.4 K < T < 140 K) and Mössbauer spectroscopy (10 K < T < 290 K). Rather small atom displacement parameters for the Ba filler atoms indicate a severe reduction in the “rattling behaviour” consistent with the high levels of lattice thermal conductivity. The elastic moduli, collected from Resonant Ultrasonic Spectroscopy ranged from 100 GPa for Ni 4 Sb 8.2 Sn 3.8 to 116 GPa for Ba 0.92 Ni 4 Sb 6.7 Sn 5.3 . The thermal expansion coefficients were 11.8 × 10 -6 K -1 for Ni 4 Sb 8.2 Sn 3.8 and 13.8 × 10 -6 K -1 for Ba 0.92 Ni 4 Sb 6.7 Sn 5.3 . The room temperature Vickers hardness values vary within the range from 2.6 GPa to 4.7 GPa. Lastly, severe plastic deformation via high-pressure torsion was used to introduce nanostructuring; however, the physical properties before and after HPT showed no significant effect on the materials thermoelectric behaviour.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Balancing structural distortions via competing 4f and itinerant interactions: A case of polymorphism in magnetocaloric HoCo 2

The nature of multiple magnetostructural transformations in HoCo 2 has been studied by employing magnetic and specific heat measurements, temperature and magnetic field dependent X-ray powder diffraction, and first-principles calculations. Unexpected increase of magnetization observed below the spin-reorientation temperature (T SR ) suggests that the low-temperature transition involves a reduction of Co moment. First principles calculations confirm that the paramagnetic cubic to ferrimagnetic tetragonal transformation at T C is assisted by itinerant electron metamagnetism, and that the reduction of Co moment in HoCo 2 occurs in parallel with the ferrimagnetic tetragonal to the nearly ferromagnetic orthorhombic transformation at T SR via the rearrangement of both 3d states of Co and 5d states of Ho. The ac magnetic susceptibility measurements show significant magnetic frustration below T C . Furthermore, in contrast to earlier reports neither ac nor dc magnetic susceptibilities show anomalies in the paramagnetic region obeying the Curie–Weiss law.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Anisotropy induced anomalies in Dy 1$-$x Tb x Al 2

The Dy 1$-$x Tb x Al 2 alloys have been investigated by X-ray powder diffraction, heat capacity, and magnetic measurements. All samples exhibit cubic Laves phase crystal structure at room temperature but at T C , DyAl2 and TbAl 2 show tetragonal and rhombohedral distortions, respectively. First order phase transitions are observed below T C (at the spin-reorientation transition, T SR ) in the alloys with 0.15 ≤ x ≤ 0.35. These transitions are signified by sharp heat capacity peaks and corresponding anomalies in the magnetization and ac magnetic susceptibility data. The observations are interpreted by taking into consideration the differences in easy magnetization directions of DyAl 2 and TbAl 2 . Due to the competing magnetic structures, the anisotropy-related instability and magnetic frustrations are prominent in the Dy 1$-$x Tb x Al 2 alloys at certain concentrations resulting in the first order transitions.

36 MATERIALS SCIENCE↗