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Results for “Metal coordination”

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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Advanced LiFSI-LiPF6 Electrolyte for Wide-Temperature and Thermally Stable Lithium-Ion Batteries

A new optimized LiFSI–LiPF6 dual-salt controlled-solvation electrolyte (E-DS) is demonstrated to enable practical graphite||LiNi0.8Mn0.1Co0.1O2 cells (˜4.0 mAh cm?²) to achieve exceptional performance and safety under extreme conditions. By optimizing anion coordination with the smaller, more dissociating FSI? anion, the E-DS forms ultrathin, dense, and inorganic-rich electrode/electrolyte interphases that dramatically suppress solvent decomposition, transition-metal dissolution, and surface reconstruction compared to the conventional LiPF6/carbonate electrolyte. Consequently, E-DS cells deliver >78% capacity retention after 300 cycles at 60 °C, retain fast discharging capacity at 30 °C, and operate effectively at -20 °C. Most strikingly, fully charged full cells with E-DS, even under overcharging to 4.8 V, show a lower heat evolution in stable formulations — transforming a traditionally unstable high-voltage/high-temperature configuration into an intrinsically safe state. This work establishes a new benchmark for carbonate-containing electrolytes, simultaneously achieving high energy density, fast-discharging capability, wide-temperature operation (-20 to 60 °C), and outstanding thermal safety in nickel-rich lithium-ion batteries.

electrode/electrolyte interphase↗
DOE OSTI2021

Intervening Oxygen Enabled Magnetic Moment Modulation in Spinel Nanostructures

Oxygen vacancies and lattice oxygen on the surface of nanoparticles play crucial roles in the magnetism of transition metal oxides. A fundamental understanding of the interactions between the 2p orbitals of oxygen anions and the 3d orbitals of metal cations is of immense interest for applications due to specific electronic, magnetic, and chemical properties. The spinel nanostructures Co 3 O 4 ,Fe 3 O 4 , and CoFe 2 O 4 present a unique model to alter coordination and bonding due to d electrons and oxygen 2p states. We performed complementary experimental techniques and corresponding model calculations to show that the overall net magnetism differs significantly between the O 2 -rich and -deficient environments. It was found that in monometallic spinel oxides (e.g., Co 3 O 4 and Fe 3 O 4 ), the changes in the spin moment are relatively small (~0.08μ B per formula unit) compared to those in the bimetallic spinel oxide CoFe 2 O 4 (~0.40 μ B per formula unit). Finally, our study illustrates that the O 2 -rich/deficient conditions alter the exchange of O h sites and adjust the metal ion moments so as to impact the overall magnetism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Finite-Temperature Structures of Supported Subnanometer Catalysts Inferred via Statistical Learning and Genetic Algorithm-Based Optimization

Single-atom catalysts (SACs) minimize noble metal utilization and can alter the activity and selectivity of supported metal nanoparticles. However, the morphology of active centers, including single atoms and subnanometer clusters of a few atoms, remains elusive due to experimental challenges. The computational cost to describe numerous cluster shapes and sizes makes direct first-principles calculations impractical. We present a computational framework to enable structure determination for single-atom and subnanometer cluster catalysts. As a case study, we obtained the low energy structures of Pd n (n = 1-21) clusters supported on CeO 2 (111), which are critical components of automobile three-way catalysts. Trained on density functional theory data, a three-dimensional cluster expansion is established using statistical learning to describe the Hamiltonian and predict energies of supported Pdn clusters of any structure. Low energy stable and metastable structures are identified using a Metropolis Monte Carlo-based genetic algorithm in the canonical ensemble at 300 K. We observe that supported single atoms sinter to form bilayer clusters and large cluster isomers share similarities in both shape and energy, and elucidate the significance of the support and microstructure on cluster stability. We discovered a simple surrogate structure-energy model, where the energy per atom scales with the square root of the average first coordination number, which can be used to estimate energies and compare the stability of clusters. Our framework, applicable to any metal/support system, fills an important methodological gap to predict the stability of supported metal catalysts in the subnanometer regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Metal-ligand interactions in a redox active ligand system. Electrochemistry and spectroscopy of [M(dipyvd) 2 ] n+ (M=Zn, Ni, n =0, 1, 2)

Reaction of nickel and zinc triflates with the tridentate leucoverdazyl 1-isopropyl-3,5-di (2'-pyridyl)-6-oxo-2H-tetrazine (dipyvdH) and triethylamine resulted in the neutral coordination compounds M(dipyvd) 2 (M = Ni,Zn). In acetonitrile, both compounds undergo two one electron oxidation processes, Zn (dipyvd) 2 at -0.28 V and -0.12 V and Ni(dipyvd) 2 at -0.32 V and -0.15 V vs ferrocene/ferricenium. Oxidations are ligand based resulting in an intermediate mixed valence species and a cationic bis(verdazyl) compound respectively. Oxidation of the ligand changes a localized, antiaromatic, non-planar 8π electron anion to a planar, delocalized 7π electron radical. The change in ligand structure results in an increase in the octahedral ligand field splitting from 10,500 cm –1 to ~13,000 cm –1 , suggesting an increase in the pi acceptor character of the ligand. In the mixed valence species, spectroscopic data suggests minimal interaction between ligands mediated by the metal center; i.e., these are class I-II systems in the Robin-Day classification.

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

Continuity of reaction kinetics across the pressure and materials gaps in CO oxidation on FeO–Pt interfaces

Translating atomic-scale insights from surface science studies of model catalysts to practical powder catalysts remains a persistent challenge in heterogeneous catalysis. Here, in this study, we demonstrate mechanistic continuity across the pressure and materials gaps during CO oxidation at the FeO-Pt interface using in situ microscopy, spectroscopy and computational modelling. Under reaction conditions, coordinatively unsaturated Fe (Fe cus ) sites at the interface enable selective O 2 activation on CO-saturated surfaces, circumventing the CO-poisoning limitation of platinum-group metals. We identify parallel reaction pathways involving the *O 2 -*CO intermediate. Remarkably, activation energies remain consistent at 12-15 kJ mol −1 (0.12-0.16 eV) from ultrahigh vacuum to atmospheric pressures and from FeO/Pt(111) model catalysts to FeO/Pt powder catalysts, validating mechanistic insights derived from surface science studies. Our findings show an example of bridging the long-standing divide between model and practical catalyst systems, establishing an effective approach to capture catalytic behaviours under operational conditions and advancing mechanism-driven catalyst design.

03 NATURAL GAS↗
NASA NTRS1985

Crystal Chemistry of Meteoritic Hibonites

The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinates. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

Burns, R. G.↗
NASA NTRS1984

Crystal chemistry of meteoritic hibonites

The characteristics of cation vacancies and site occupancies of natural hibonites in meteors are discussed. Note is taken of the effect of the specific locations of the hibonites in the matrices on the crystal chemistry, electronic stabilities, and spectral features of the metal ions which replace the Al(3+). Hibonites form beta-alumina hexagonal cells with 26 cation sites. Fe cations are found in octahedral, tetrahedral, and five-fold coordinations. Fe(2+) is found in face-shared Al(3) octahedra, a siting explained in terms of ionic radius and crystal field stabilization energy criteria. Spectral colors are attributed to V(3+) and Ti(3+) field transitions at 400 and 700 nm, respectively, although the 700 nm line may arise from transitions of Ti(3+) to Ti(4+) or Fe(2+) to Fe(3+) during heating. Excesses of Mg-26 can be traced to decay of nebular Al-26.

Burns, R. G.↗
NASA NTRS1993

Feasibility study of a synthesis procedure for array feeds to improve radiation performance of large distorted reflector antennas

There were several tangible products that resulted from the reflector antenna research program. The initial technical effort was to develop techniques to compensate for distortions over the surface of the main reflector of a large reflector antenna system. An in-depth investigation of this problem resulted in a new technique for the electronic correction of surface errors. A journal article on the findings describe the use of the iterative sampling method. Shortly after the 'Mission to Planet Earth' program started, we began investigating the use of large reflector antennas in geostationary orbit for passive earth remote sensing. A study panel was coordinated by Virginia Tech to set technical goals for the effort. These were used to guide the design of several antennas. The original interest stemmed from an industrial (Reynolds Metals) need and currently involves work with industry (Prodelin Corporation) on high technology, low cost reflectors. The intervening years (1987 - 1993) is the period of this report and Virginia Tech's reflector antenna activity then was exclusively with NASA LaRC.

Stutzman, W. L.↗
DOE OSTI2022

Prussian blue derived catalysts

Prussian blue analog derived catalysts having a composition of highly porous transition metal (“TM”) oxides with nano particle size. Such OER catalysts are synthesized from the PBA, containing cobalt, iron, nickel, copper, manganese, zinc, magnesium etc., as secondary building units (“SBUs”) coordinated by hexacyano-based ligands. Furthermore, the PBA-derived catalysts may also integrated into a highly graphitized carbon network to further improve the conductivity, mass transport and durability against oxidative corrosion.

Liu, Di-Jia↗
DOE OSTI2025

Local order, disorder, and everything in between: using 91 Zr solid-state NMR spectroscopy to probe zirconium-based metal–organic frameworks

Characterization of metal centers in metal–organic frameworks (MOFs) is critical for rational design and further understanding of structure–property relationships. The short-range structure about Zr atoms is challenging to properly elucidate in many Zr MOFs, particularly when local disorder is present. Static 91 Zr solid-state NMR spectra of the seven zirconium MOFs UiO-66, UiO-66-NH 2 , UiO-67, MOF-801, MOF-808, DUT-68 and DUT-69 have been acquired at high magnetic fields of 35.2 T and 19.6 T, yielding valuable information on the local structure, site symmetry and order about Zr. 91 Zr NMR is very sensitive to differences in MOF short-range structure caused by guest molecules, linker substitution and post-synthetic treatment. Complementary density functional theory (DFT) calculations assist in the interpretation and assignment of 91 Zr solid-state NMR spectra, lend insight into structural origins of 91 Zr NMR parameters and enable determination of local Zr coordination environments. This approach can be extended to many other materials containing zirconium.

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

Temperature–Programmed Separation of Hexane Isomers by a Porous Calcium Chloranilate Metal–Organic Framework

The full separation of alkane isomers as a function of different degrees of branching remains a daunting challenge due to its stringent requirement with respect to pore dimensions of the adsorbents. In this work, we report a novel microporous coordination network built on calcium (II) and chloranilate. The compound has a flexible framework and exhibits temperature-dependent adsorption behavior toward hexane isomers. At 30 °C, it accommodates substantial amounts of linear and monobranched hexanes but fully excludes their dibranched isomer, and at elevated temperatures such as 150 °C, it acts as a splitter for linear and branched alkanes. Its capability of efficient discrimination of hexane isomers as a function of branching is verified by experimental breakthrough measurements. Furthermore, ab initio calculations have uncovered the underlying selective size-exclusion separation mechanism.

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

Electronically-coupled redox centers in trimetallic cobalt complexes

Synthesis and isolation of molecular building blocks of metal–organic frameworks (MOFs) can provide unique opportunities for characterization that would otherwise be inaccessible due to the heterogeneous nature of MOFs. Herein, we report a series of trinuclear cobalt complexes incorporating dithiolene ligands, triphenylene-2,3,6,7,10,11-hexathiolate (THT) (1 3+ ), and benzene hexathiolate (BHT) (2 3+ ), with 1,1,1,-tris(diphenylphosphinomethyl)ethane (triphos) employed as the capping ligand. Single crystal X-ray analyses of 1 3+ and 2 3+ display three five-coordinate cobalt centers bound to the triphos and dithiolene ligands in a distorted square pyramidal geometry. Cyclic voltammetry studies of 1 3+ and 2 3+ reveal three redox features associated with the formation of mixed valence states due to the sequential reduction of the redox-active metal centers (Co III/II ). Using this electrochemical data, the comproportionality values were determined for 1 and 2 (log K c = 1.4 and 1.5 for 1, and 4.7 and 5.8 for 2), suggesting strong resonance-stabilized coupling of the metal centers, with stronger electronic coupling observed for complex 2 compared to that for complex 1. Cyclic voltammetry studies were also performed in solvents of varying polarity, whereupon the difference in the standard potentials (ΔE 1/2 ) for 1 and 2 was found to shift as a function of the polarity of the solvent, indicating a negative correlation between the dielectric constant of the electrochemical medium and the stability of the mixed valence species. Spectroelectrochemical studies of in situ generated multi-valent (MV) states of complexes 1 and 2 display characteristic NIR intervalence charge transfer (IVCT) bands, and analysis of the IVCT transitions for complex 2 suggests a weakly coupled class II multi-valent species and relatively large electronic coupling factors (1700 cm –1 for the first multi-valent state of 2 2+ , and 1400 and 4000 cm –1 for the second multi-valent state of 2 + ). Here, density functional theory (DFT) calculations indicate a significant deviation in relative energies of the frontier orbitals of complexes 1 3+ , 2 3+ , and 3 + that contrasts those calculated for the analogous trinuclear cobalt dithiolene complexes employing pentamethylcyclopentadienyl (Cp*) as the capping ligand (Co 3 Cp* 3 THT and Co 3 Cp* 3 BHT, respectively), and may be a result of the cationic nature of complexes 1 3+ , 2 3+ , and 3 + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Crystallographic Evidence for Formation of M 6 O 8 /M 6 O 9 f-Element Clusters in Hydrolysis Reactions

In this contribution, we have conducted an examination of crystallographic data which includes 184 4f- and 5f-structures containing the M 6 O 8 or M 6 O 9 moiety. Since much of the work in this field has actually been done to explore the formation and properties of metal organic frameworks (MOFs), we hope that this collection can be used by actinide scientists to further investigate structural and mechanistic trends and gain insight into the formation of these compounds. Here we discuss the general trends in coordination, ligands used, and bonding within the M 6 O 8 or M 6 O 9 core in the hope that further computational work can benefit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Copper-containing layered oxide cathodes for sodium-ion batteries

Layered transition metal oxides are among the most promising cathode materials for sodium-ion batteries due to their high theoretical capacity, structural tunability, and cost-effectiveness. However, conventional Ni- and Co-based layered oxides are hindered by high raw material costs, limited elemental abundance, and phase instability during electrochemical cycling. Recently, copper has emerged as an attractive alternative transition metal, offering significant advantages in terms of redox activity, structural stabilization, voltage regulation, and rate performance. Unlike Ni and Co, Cu can facilitate unique redox mechanisms and enable more sustainable material design. This review systematically summarizes recent progress on Cu-containing layered sodium oxides, with emphasis on their structural characteristics, electrochemical behavior, and the critical roles that Cu plays within the host lattice. The insights provided herein aim to highlight the potential of Cu-substituted or Cu-containing layered oxides as a viable pathway toward high-performance and resource-accessible SIB cathodes for future energy storage applications.

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

Synthetic Control of Water-Stable Hybrid Perovskitoid Semiconductors

Hybrid metal-halide perovskites and their derived materials have emerged as the next-generation semiconductors with a wide range of applications, including photovoltaics, light-emitting devices, and other optoelectronics. Over the past decade, numerous single-crystalline perovskite derivatives have been synthesized and developed. However, the synthetic methods for these derivatives mainly rely on acidic crystallization conditions. This approach leads to crystals comprising metal halide building blocks, which show problematic stability when directly exposed to water. In this study, a methodology is developed for synthesizing hybrid metal-halide compounds using lead iodide and the zwitterionic bifunctional molecule cysteamine (CYS), to form various perovskitoid structures under a broad pH range. Interestingly, the different pH conditions alter the coordination environment of lead halides, leading to lead-sulfide and lead-nitride covalent bond formation. This modification significantly enhances their stability when in direct contact with water, lasting for months. Photoluminescence measurements and first principal density functional theory (DFT) calculations reveal that the perovskitoids synthesized under basic and acidic pH conditions exhibit a direct bandgap nature, while those synthesized under neutral conditions display an indirect bandgap. This approach opens new avenues for manipulating synthetic methods to develop water-stable hybrid semiconductors suitable for a wide range of applications, such as solid-state light emitters.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Ultrafast snapshots of terahertz electric potentials across ring-shaped quantum barriers

Probing the time evolution of the terahertz electric field within subwavelength dimensions plays a crucial role in observing the nanoscale lightwave interactions with fundamental excitations in condensed-matter systems and in artificial structures, such as metamaterials. Here, we propose a novel probing method for measuring terahertz electric potentials across nanogaps using a combination of optical and terahertz pulse excitations. To achieve this, we employ ring-shaped nanogaps that enclose a metallic island, allowing us to capture tunneling charges when subjected to terahertz electromagnetic pulse illumination. By controlling and manipulating the terahertz tunneling charges through a focused optical gate pulse, we can obtain the terahertz potential strength as a function of spatial coordinates and time delays between pulses. To accurately quantify the time evolution of terahertz electric potential across quantum barriers, we carefully calibrate the recorded nonlinear tunneling current. Its on-resonance and off-resonance behaviors are also discussed, providing valuable insights into the antenna’s characteristics and performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C 3+ Olefin Formation from Ethanol

Direct and selective production of C 3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. In this study, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C 3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde C═C bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H 2 ) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10 –3 mol mol Y –1 s –1 vs 1.2 × 10 –3 mol mol Zn –1 s –1 ). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C 3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗