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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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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Predicting kinetics of polymorphic transformations from structure mapping and coordination analysis

To extend materials design and discovery into the space of metastable polymorphs, rapid and reliable assessment of transformation kinetics to lower energy structures is essential. Herein we focus on diffusionless polymorphic transformations and investigate routes to assess their kinetics using solely crystallographic arguments. As part of this investigation we developed a general algorithm to map crystal structures onto each other, and ascertain the low-energy (fast-kinetics) transformation pathways between them. Pathways with minimal dissociation of chemical bonds, along which the number of bonds (in ionic systems the first-shell coordination) does not decrease below that in the end structures, are shown to always be the fast-kinetics pathways. These findings enable the rapid assessment of the kinetics of polymorphic transformation and the identification of long-lived metastable structures. In conclusion, the utility is demonstrated on a number of transformations including those between high-pressure SnO 2 phases, which lack a detailed atomic-level understanding.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Crystal structure of the layered arsenide Rb 3 Cu 3 As 2

The crystal structure of a new arsenide, Rb 3 Cu 3 As 2 (trirubidium tricopper diarsenide), has been established from single-crystal X-ray diffraction data. This compound crystallizes in the K 3 Cu 3 P 2 type, with layers of interlinked CuAs 2 units. The partitioning of the available valence electrons yields the charge-balanced composition (Rb + ) 3 (Cu + ) 3 (As 3– ) 2 , placing this phase in a broad field of transition-metal-containing Zintl phases. First-principles calculations confirm a semiconducting ground state, in accordance with electron-counting considerations. Chemical bonding analysis reveals strong covalent Cu—As bonds and ionic Rb...As interactions. In addition, a weak attraction is found between the Cu atoms, possibly pointing toward cuprophilic interactions.

Chemistry↗
DOE OSTI2023

Expeditious Coordination-Driven Construction of Hierarchically Nanoporous Barium Salts

Organic moieties-derived salts with permanent porosity and polarized channels have shown unique features and attractive performance in the field of adsorption, separation, and conduction. However, state-of-the-art organic salts generally rely on ionic interaction and hydrogen bonding formation to maintain the porous channels. The synthesis of organic moiety-derived salts with permanent accessible pores even after removal of the trapped guest molecules, and without the constraint of hydrogen bonding formation still remains a great challenge. Herein, we present an expeditious construction pathway to generate hierarchically nanoporous barium salts without hydrogen bonding formation. The strong ionic interaction of the barium cation and sulfonate anions led to rapid reaction equilibrium (~2 min), affording diverse barium-derived ionic polymer (Ba-IP) with permanent porosity and highly polarized channels. The produced Ba-IP materials with abundant cations and anions displayed high CO 2 /N 2 and CO 2 /CH 4 separation performance, with the selectivities reaching up to 89.5 and 280, respectively, at 273 K, surpassing most of the organic polymers functionalized by ionic moieties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Computer-aided design of polymers and composites

This book on computer-aided design of polymers and composites introduces and discusses the subject from the viewpoint of atomic and molecular models. Thus, the origins of stiffness, strength, extensibility, and fracture toughness in composite materials can be analyzed directly in terms of chemical composition and molecular structure. Aspects of polymer composite reliability are considered along with characterization techniques for composite reliability, relations between atomic and molecular properties, computer aided design and manufacture, polymer CAD/CAM models, and composite CAD/CAM models. Attention is given to multiphase structural adhesives, fibrous composite reliability, metal joint reliability, polymer physical states and transitions, chemical quality assurance, processability testing, cure monitoring and management, nondestructive evaluation (NDE), surface NDE, elementary properties, ionic-covalent bonding, molecular analysis, acid-base interactions, the manufacturing science, and peel mechanics.

Kaelble, D. H.↗
DOE OSTI2023

Americium Oxalate: An Experimental and Computational Investigation of Metal–Ligand Bonding

A novel actinide-containing coordination polymer, [Am(C 2 O 4 )(H 2 O) 3 Cl] (Am-1), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional and comprised of pseudo-dimeric Am 3+ nodes that are bridged by oxalate ligands to form sheets. Each metal center is nine-coordinate, forming a distorted capped square antiprism geometry with a C 1 symmetry, and features bound oxalate, aqua, and chloro ligands. The Am 3+ –ligand bonds were probed computationally using the quantum theory of atoms in molecules nd natural localized molecular orbital approaches to investigate the underlying mechanisms and hybrid atomic orbital contributions therein. The analyses indicate that the bonds within Am-1 are predominantly ionic and the 5f shell of the Am 3+ metal centers does not add a significant covalent contribution to the bonds. Further, our bonding assessment is supported by measurements on the optical properties of Am-1 using diffuse reflectance and photoluminescence spectroscopies. The position of the principal absorption band at 507 nm ( 5 L 6' ← 7 F 0' ) is notable because it is consistent with previously reported americium oxalate complexes in solution, indicating similarities in the electronic structure and ionic bonding. Compound Am-1 is an active phosphor, featuring strong bright-blue oxalate-based luminescence with no evidence of metal-centered emission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Transition metal oxides - CrO, MoO, NiO, PdO, AgO

The transition-metal oxides are quite ionic; Mulliken population analyses for several oxides give a negative charge of about 0.7 electrons for oxygen. When the transition-metal d shell is only partially filled, the orbitals are involved in covalent bonds with O; both two-electron bonding (2)-antibonding (0) and one-electron bonding (2)-antibonding (1) bonds are formed. These covalent bonds occur in addition to the ionic bonding. There is d-sigma-O2 p sigma repulsion, and this repulsion is reduced when the d-sigma electron is promoted into an orbital which has dominantly 4sp-sigma character and is polarized away from O.

Bauschlicher, C. W., Jr.↗
DOE OSTI2020

Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding

The observation and characterization of the anions: Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – is reported. These species were studied through a synergetic combination of anion photoelectron spectroscopy and ab initio correlated molecular orbital theory calculations at the CCSD(T) level with large correlation-consistent basis sets. To better understand the energetics and bonding in these anions and their corresponding neutrals, a range of smaller diatomic to tetratomic species were studied computationally. Correlated molecular orbital theory calculations at the CCSD(T) level showed that in most of these cases, there are close-lying anions and neutral clusters with different geometries and spin states and are consistent with the experimentally observed spectra. Thus, comparison of experimentally determined and computationally predicted vertical detachment energies and electron affinities for different optimized geometries and spin states shows excellent agreement to within 0.1 eV. The structures for both the neutrals and anions have a significant ionic component to the bonding because of the large electron affinity of the Au atom and modest ionization potentials for Th 2 , Th 2 O, and Th 2 O 2 . The analysis of the bonding for the Th–Th bonds from the molecular orbitals is consistent with this ionic model. The results show that there is a wide variation in the bond distance from 2.7 to 3.5 Å for the Th–Th bonds all of which are less than twice the atomic radius of Th of 3.6 Å. The bond distances encompass bond orders from 4 to 0. Furthermore, there can be different bond orders for the same bond distance depending on the nature of the ionic bonding suggesting that one may not be able to correlate the bond order with the bond distance in these types of clusters. In addition, the presence of an Au atom may provide a unique probe of the bonding in such clusters because of its ability to accept an electron from clusters with modest ionization potentials.

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

Impact of Hydrogen Bonding on the Dynamics and Structure of Protic Ionic Liquid/Water Binary Mixtures

In this work, the orientational dynamics and microscopic liquid structure of a protic ionic liquid, 1- ethylimidazolium bis(trifluoromethylsulfonyl)imide (EhimNTf 2 ), and its aprotic analogue, 1- ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf 2 ), were studied at various water concentrations using optical heterodyne-detected optical Kerr Effect (OHD-OKE) spectroscopy, linear infrared spectroscopy, and atomistic simulations. The OHD-OKE experiments essentially measure the orientational relaxation of the Ehim + and Emim + cations. The experiments and simulations show a significant dynamical and structural change in EhimNTf 2 between the 2:1 ion pair:water and the 1:1 ion pair:water concentrations. The OHDOKE data show that EmimNTf 2 /water mixtures exhibit hydrodynamic behavior at all water concentrations up to saturation. In contrast, EhimNTf 2 /water mixtures deviate from hydrodynamic dynamic behavior at water concentrations above 2:1. At the 1:1 concentration, the orientational randomization of the Ehim + cation is slower than that predicted using viscosity data. Atomistic simulation results reveal the microscopic ionic structures of dry liquids and the preferential hydrogen bonding of water to the H atom of the N-H of Ehim + over other sites on the Ehim + and Emim + cations. Atomistic simulation results demonstrate that in EhimNTf 2 RTIL/water mixtures there is a substantial jump in the formation of water-water hydrogen bonds in addition to N-H-water hydrogen bonds upon increasing the water concentration from 2:1 to 1:1. Water-water hydrogen bonding strengthens the spatial coordination of the H atom of the N-H moiety of Ehim + to neighboring water molecules through preferential hydrogen bonding. The jump in the concentration of water-water hydrogen bonds occurs at the Ehim + /water concentration at which the orientational relaxation deviates from hydrodynamic behavior. This structural observation is confirmed with FT-IR spectra that show asymmetry in the peak for the O-D stretch that is indicative of water clusters. The formation of water clusters and the strengthening of the N-H … OH 2 hydrogen bonds slow the orientational relaxation of Ehim + cations as observed by the OHD-OKE experiments.

14 SOLAR ENERGY↗
DOE OSTI2019

Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids

Functionalization of the imidazolium (Im + ) cationic component of ionic liquids (ILs) with ether chains affords the possibility of tuning their properties through manipulation of the resulting inter-ion and intramolecular interactions. Herein, we quantify these interactions at the molecular level through analysis of the vibrational spectra displayed by size-selected and cryogenically-cooled ions. These spectra are obtained using the “tagging” approach carried out with photofragmentation tandem mass spectrometry. In the isolated cations, we find that the oxygen atom on the ether chain binds exclusively to the acidic C (2) H position on the Im + ring. Upon complexation with BF 4 ¯ to form the ternary (Ether-MIm + ) 2 (BF 4 ¯) cation, however, the less acidic C (4,5) H groups also participate as contact points for the ionic assembly, in contrast to the behavior of the closely related (EMIm + ) 2 (BF 4 ¯) system. Furthermore, these experimental results support the conclusions derived from earlier X-ray scattering and molecular dynamics results on bulk ILs regarding interactions with the ring CH groups and their implications on tuning the viscosities of this class of functionalized ILs.

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

The carbon challenge: Design, synthesis, and chemisorption behavior of solid sorbents in direct air capture of carbon dioxide

Direct air capture (DAC) of CO 2 is a promising solution for reducing the carbon footprint through "negative emission" technology. However, the low CO 2 concentration (~400 ppm) and the dynamic nature of DAC processes present challenges in designing effective sorbent systems. Recent advancements in material design and structural engineering have led to the development of high-performance solid sorbents, offering a more stable, safe, and energy-efficient alternative to traditional liquid CO 2 capture methods. This review highlights progress in solid sorbent-based DAC, focusing on amine-modified materials, hydrogen-bonded frameworks, and ionic liquid-engineered scaffolds. The discussion covers design principles, synthesis methodologies, and their impact on CO 2 chemisorption, comparing the advantages and limitations of each approach. Characterization techniques, especially operando methods and computational tools, are reviewed to understand sorbent behavior during CO 2 integration and release. The reaction pathways and interaction mechanisms of these sorbents with CO 2 are analyzed to guide future design. Additionally, the CO 2 chemisorption behaviors, including capacity, sorption kinetics, recyclability, and durability in the presence of gaseous impurities and under humid conditions will be evaluated and compared. Further, the review offers unique insights into the physical properties, chemical structures, and surface engineering effects of these sorbents, based on comprehensive characterization and evaluation techniques.

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

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO 2 Cathodes

Abstract The O‐type layered nickel oxides suffer from undesired cooperative Jahn–Teller distortion stemming from Ni 3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na + ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg 2+ ) or trivalent (Al 3+ or Co 3+ ) ions for Ni 3+ to alleviate Na + ion ordering and perturb the Jahn–Teller effect to enhance structural stability. We gauge a fundamental understanding of the Mg−O and Na−O or Mg−O−Na bonding interactions, noting that the ionicity of the Mg−O bond deshields the electronic cloud of oxygen from Na + ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO 6 octahedra from Jahn–Teller distortion and a reduced electron density at the interlayer with Mg 2+ substitution. Long‐range ( operando X‐ray diffraction) and short‐range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg‐substitution results in a high‐capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium‐ion batteries.

Sada, Krishnakanth↗
DOE OSTI2024

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO 2 Cathodes

The O-type layered nickel oxides suffer from undesired cooperative Jahn–Teller distortion stemming from Ni 3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na + ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg 2+ ) or trivalent (Al 3+ or Co 3+ ) ions for Ni 3+ to alleviate Na + ion ordering and perturb the Jahn–Teller effect to enhance structural stability. Here, we gauge a fundamental understanding of the Mg−O and Na−O or Mg−O−Na bonding interactions, noting that the ionicity of the Mg−O bond deshields the electronic cloud of oxygen from Na + ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO 6 octahedra from Jahn–Teller distortion and a reduced electron density at the interlayer with Mg 2+ substitution. Long-range (operando X-ray diffraction) and short-range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg-substitution results in a high-capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

A Crosslinked Ionic Organic Framework for Efficient Iodine and Iodide Remediation in Water

Iodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (~5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer-directed synthesis of a single-crystalline ionic hydrogen-bonded crosslinked organic framework (HCOF-7). HCOF-7 removes iodine and iodide species in water efficiently through halogen bonding and anion exchange, reducing the total iodine concentration to 0.22 ppm at room temperature. Packed HCOF-7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L/g). Finally, the high iodine/iodide removal benchmarks recorded under practical conditions make HCOF-7 a promising adsorbent for water treatment.

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

Experimental and Computational Description of the Interaction of H and H – with U

In this work, the results of ab initio correlated molecular orbital theory electronic structure calculations for low-lying electronic states are presented for UH and UH – and compared to photoelectron spectroscopy measurements. The calculations were performed at the CCSD(T)/CBS and multireference CASPT2 including spin–orbit effects by the state interacting approach levels. The ground states of UH and UH – are predicted to be 4 Ι 9/2 and 5 Λ 6 , respectively. The spectroscopic parameters T e , r e , ω e , ω e x e , and Be were obtained, and potential energy curves were calculated for the low energy Ω states of UH. The calculated adiabatic electron affinity is 0.468 eV in excellent agreement with an experimental value of 0.462 ± 0.013 eV. The lowest vertical detachment energy was predicted to be 0.506 eV for the ground state, and the adiabatic ionization energy (IE) is predicted to be 6.116 eV. The bond dissociation energy (BDE) and heat of formation values of UH were obtained using the IE calculated at the Feller–Peterson–Dixon level. For UH, UH – , and UH + , the BDEs were predicted to be 225.5, 197.9, and 235.5 kJ/mol, respectively. The BDE for UH is predicted to be ~20% lower in energy than that for ThH. The analysis of the natural bond orbitals shows a significant U + H – ionic component in the bond of UH.

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

Porous liquid zeolites: hydrogen bonding-stabilized H-ZSM-5 in branched ionic liquids

Porous liquids, as a newly emerging type of porous material, have great potential in gas separation and storage. However, the examples and synthetic strategies reported so far likely represent only the tip of the iceberg due to the great difficulty and challenge in engineering permanent porosity in liquid matrices. By taking advantage of the hydrogen bonding interaction between the alkane chains of branched ionic liquids and the Brønsted sites in H-form zeolites, as well as the mechanical bond of the long alkyl chain of the cation penetrated into the zeolite channel at the interface, the H-form zeolites can be uniformly stabilized in branched ionic liquids to form porous liquid zeolites, which not only significantly improve their gas sorption performance, but also change the gas sorption–desorption behavior because of the preserved permanent porosity. Furthermore, such a facile synthetic strategy can be extended to fabricate other types of H-form zeolite-based porous liquids by taking advantage of the tunability of the counter-anion (e.g., NTf 2 - , BF 4 - , EtSO 4 - , etc.) in branched ionic liquids, thus opening up new opportunities for porous liquids for specific applications in energy and environment.

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

Shape Persistent, Highly Conductive Ionogels from Ionic Liquids Reinforced with Cellulose Nanocrystal Network

Abstract Shape‐persistent, conductive ionogels where both mechanical strength and ionic conductivity are enhanced are developed using multiphase materials composed of cellulose nanocrystals and hyperbranched polymeric ionic liquids (PILs) as a mechanically strong supporting network matrix for ionic liquids with an interrupted ion‐conducting pathway. The integration of needlelike nanocrystals and PIL promotes the formation of multiple hydrogen bonding and electrostatic ionic interaction capacitance, resulting in the formation of interconnected networks capable of confining a high amount of ionic liquid (≈95 wt%) without losing its self‐sustained shape. The resulting nanoporous and robust ionogels possess outstanding mechanical strength with a high compressive elastic modulus (≈5.6 MPa), comparable to that of tough, rubbery materials. Surprisingly, these rigid materials preserve the high ionic conductivity of original ionic liquids (≈7.8 mS cm −1 ), which are distributed within and supported by the nanocrystal network‐like rigid frame. On the one hand, such stable materials possess superior ionic conductivities in comparison to traditional solid electrolytes; on the other hand, the high compression resistance and shape‐persistence allow for easy handling in comparison to traditional fluidic electrolytes. The synergistic enhancement in ion transport and solid‐like mechanical properties afforded by these ionogel materials make them intriguing candidates for sustainable electrodeless energy storage and harvesting matrices.

Lee, Hansol↗
DOE OSTI2018

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.

ab initio molecular 8 dynamics↗