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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of CuI complexes with N-heterocyclic diazoolefin ligands. Furthermore, the complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.

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

Data-driven design of molecular nanomagnets

Three decades of research in molecular nanomagnets have raised their magnetic memories from liquid helium to liquid nitrogen temperature thanks to a wise choice of the magnetic ion and coordination environment. Still, serendipity and chemical intuition played a main role. In order to establish a powerful framework for statistically driven chemical design, here we collected chemical and physical data for lanthanide-based nanomagnets, catalogued over 1400 published experiments, developed an interactive dashboard (SIMDAVIS) to visualise the dataset, and applied inferential statistical analysis. Our analysis shows that the Arrhenius energy barrier correlates unexpectedly well with the magnetic memory. Furthermore, as both Orbach and Raman processes can be affected by vibronic coupling, chemical design of the coordination scheme may be used to reduce the relaxation rates. Indeed, only bis-phthalocyaninato sandwiches and metallocenes, with rigid ligands, consistently present magnetic memory up to high temperature. Analysing magnetostructural correlations, we offer promising strategies for improvement, in particular for the preparation of pentagonal bipyramids, where even softer complexes are protected against molecular vibrations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Formation of Benzene and Naphthalene through Cyclopentadienyl-Mediated Radical–Radical Reactions

Resonantly stabilized free radicals (RSFRs) have been contemplated as fundamental molecular building blocks and reactive intermediates in molecular mass growth processes leading to polycyclic aromatic hydrocarbons (PAHs) and carbonaceous nanoparticles on Earth and in deep space. Here, by combining molecular beams and computational fluid dynamics simulations, we provide compelling evidence on the formation of benzene via the cyclopentadienyl-methyl reaction and of naphthalene through the cyclopentadienyl self-reaction, respectively. These systems offer benchmarks for the conversion of a five-membered ring to the 6π-aromatic (benzene) and the generation of the simplest 10π-PAH (naphthalene) at elevated temperatures. These results uncover molecular mass growth processes from the “bottom up” via RSFRs in high temperature circumstellar environments and combustion systems expanding our fundamental knowledge of the organic, hydrocarbon chemistry in our universe.

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

Exotic Reaction Dynamics in the Gas-Phase Preparation of Anthracene (C 14 H 10 ) via Spiroaromatic Radical Transients in the Indenyl–Cyclopentadienyl Radical–Radical Reaction

The gas-phase reaction between the 1-indenyl (C 9 H 7 •) and the cyclopentadienyl (C 5 H 5 •) radical has been investigated for the first time using synchrotron-based mass spectrometry coupled with a pyrolytic reactor. Soft photo-ionization with tunable vacuum ultraviolet photons afforded for the isomer-selective identification of the production of phenanthrene, anthracene, and benzofulvalene (C 14 H 10 ). The classical theory prevalent in the literature proposing that radicals combine only at their specific radical centers is challenged by our discovery of an unusual reaction pathway that involves a barrierless combination of a resonantly stabilized hydrocarbon radical with an aromatic radical at the carbon atom adjacent to the traditional C1 radical center; this unconventional addition is followed by substantial isomerization into phenanthrene and anthracene via a category of exotic spiroaromatic intermediates. Furthermore, this result leads to a deeper understanding of the evolution of the cosmic carbon budget and provides new methodologies for the bottom-up synthesis of unique spiro-aromatics that may be relevant for the synthesis of more complex aromatic carbon skeletons in deep space.

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

Lithium-Ion Battery Materials as Tunable, “Redox Non-Innocent” Catalyst Supports

The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end, herein, we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (Li x Mn 2 O 4 ) to yield isolated Ni2+ occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/Li x Mn 2 O 4 ). Additionally, the activity of Ni/Li x Mn 2 O 4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/Li x Mn 2 O 4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H 2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on Li x TiO 2 , demonstrating the generality of this phenomenon.

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

An industrial perspective on catalysts for low-temperature CO 2 electrolysis

Electrochemical conversion of CO 2 to useful products at temperatures below 100 °C are nearing the commercial scale. Pilot units for CO 2 conversion to CO are already in testing. Units to convert CO 2 to formic acid are projected to reach pilot scale in the next year. Further, several investigators are starting to observe industrially relevant rates of the electrochemical conversion of CO 2 conversion to ethanol and ethylene with the needed hydrogen coming from water. In each case, Faradaic efficiencies of 80% or more and currents above 200 mA/cm –2 can be reproducibly achieved. In this study we describe the key advances in nano catalysts that lead to the impressive performance, indicate where additional work is needed and provide benchmarks that others can use to compare their results.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Synthesis and Characterization of Uranium Complexes Supported by Substituted Aryldimethylsilylanilide Ligands

Here, we report the synthesis and characterization of substituted aryldimethylsilyldiisopropylanilide ligands and their respective bisamido complexes of U(III), (3,5-R 2 -PhMe 2 SiNDipp) 2 UI(dioxane) x (1, R = H, x= 0; 2, R = Me, x = 0; 3, R = t Bu, x = 1). We found that the steric bulk of the 3,5-R 2 -Ph ring affects the hapticity of the U–arene interaction. In the solid-state, 1 is a U–(η 6 -arene) complex, while 2 is a bis(U–(η 1 -arene)) complex. Theoretically calculated bond orders at PBE0 and PBE0-D3 levels of theory support these hapticity assignments. The 3,5- t Bu 2 -Ph rings of 3 are too bulky to interact with U and solid-state metrical parameters initially suggested a U–(η 1 -arene) interaction with one of the Dipp rings. However, bond order calculations show that this interaction is even weaker than in the previously reported ((PhMe 2 Si) 2 N) 3 U complex, leading to the conclusion that 3 is best described as a U–(η o -arene) complex. Molecular orbital analyses in conjunction with electron localization methods reveal that the U–(η 6 -arene) bonding in 1 is primarily electrostatic in nature. Some charge transfer takes place from the arene π orbitals to the U 6d/5f hybrid orbitals in addition to subtle δ-back-bonding. In 2 and 3, both π and δ interactions are substantially weaker, in agreement with the differences in the U–arene coordination modes. Surprisingly, attempts to generate less sterically bulky (3,5-R 2 -PhMe 2 SiNPh) 2 UI complexes results in disproportionation to homoleptic tetraamido (3,5-R 2 -PhMe 2 SiNPh) 4 U(IV) (4, R = H; 5, R = Me) complexes.

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

Advances in solid-state NMR for the studies of mesoporous solids: fast magic spinning and dynamic nuclear polarization

Here, this review provides an up-to-date account of the development of two solid-state (SS)NMR methods for enhancing resolution and sensitivity, fast magic angle spinning (MAS) and dynamic nuclear polarization (DNP), and the resulting progress in surface science. We demonstrate the high resolution and efficiency that can be achieved by using two-dimensional homo- and heteronuclear correlation experiments with small rotors capable of MAS at rates exceeding 100 kHz. DNP has offered significant enhancements in signal sensitivity and allowed access to nuclei and experiments that are beyond the limits of conventional SSNMR. The continuing progress in fast MAS and DNP methodologies in recent years generated an unprecedented shift in SSNMR’s capabilities in the studies of surface and interface regions of solids, especially mesoporous supports and catalysts. We give numerous examples of recent applications and discuss the prospects for further improvements of both methods.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2026

Propane Dehydrogenation Catalyzed by Supported Group IV (Ti, Zr, Hf) Organometallics on Silicon Nitride

Mesoporous silicon nitride (Si 3 N 4 ) enables access to chemisorbed group IV organometallics catalysts active for propane dehydrogenation (PDH) compared to the organometallic analogues on mesoporous silica under the same reaction conditions. The series of Si 3 N 4 -supported materials are active catalysts, (Zr > Hf > Ti k f = 290, 232, and 162 mol mol Metal -1 h -1 at 450 °C with 2% C 3 H 8 in Ar, respectively) with selectivity above 95%, demonstrating additional examples of Ti and Hf systems for PDH. However, the underlying mechanism of the improved performance relative to oxide supported homologues is not well-understood. Characterization of thermally treated samples (DRIFTS, XAS and SSNMR) and computational modeling of this catalyst series was utilized to differentiate between potential amido - (C-H activation along the M-N bond) and imido - (C-H activation along the M=N bond) mechanisms. Due to remaining mechanistic ambiguity, a Ga analogue was synthesized and evaluated for PDH activity as an indirect probe to experimentally differentiate pathways. An inversion of the oxide/nitride performance trend is observed for the Ga congener which does not form a Ga=N bond, most consistent with different mechanisms dictating the performance of the group IV/Si 3 N 4 catalysts vs Ga/Si 3 N 4 .

heterolytic cleavage↗
DOE OSTI2020

Intra- and Intermolecular Self-Assembly of a 20-nm-Wide Supramolecular Hexagonal Grid.

For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures-as opposed to polymers-have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10-100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20 nm and molecular weights greater than 65 kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers.

Zhang, Zhe↗
DOE OSTI2025

Techno-economic and life cycle analyses of the synthesis of a platinum–strontium titanate catalyst

The heterogeneous platinum/strontium titanate (Pt/SrTiO 3 or Pt/STO) catalyst has garnered significant attention as a promising candidate for the hydrogenolysis of polyolefins to hydrocarbon oils. This study evaluates the cost and environmental impacts of a newly developed scalable Pt/STO catalyst production, which includes the synthesis of the STO support and the deposition of Pt onto the support. This two-step synthesis plays a significant role in assessing the commercial feasibility of the catalyst, while energy consumption during the process plays an important role in its environmental impacts. The CatCost and the Research and Development Greenhouse Gases, Regulated Emissions, and Energy use in Technologies (R&D GREET) models were used, respectively, to perform techno-economic analysis (TEA) and life cycle analysis (LCA) of the newly developed catalyst. The TEA showed that the raw materials, accounting for approximately 76% of the total operation cost, has a profound effect on the estimated catalyst cost, mainly due to the platinum precursor. The LCA findings indicated that the catalyst production generates greenhouse gas (GHG) emissions of 66 kg CO 2 e per kg, primarily due to the use of solvents and electricity in the process. The sensitivity analysis indicated that the total operating costs (OpEX), platinum precursor cost, and spent catalyst value (SCV) significantly impact the cost of the synthesized catalyst. Additionally, adopting solvent recovery strategies and using renewable electricity can reduce the GHG emissions of catalyst production to 29 kg CO 2 e per kg.

Heterogeneous Platinum/strontium titanate Catalyst↗
NASA NTRS1974

Mass spectrometry

Review of the present status of mass spectrometry in the light of pertinent recent publications spanning the period from December 1971 to January 1974. Following an initial survey of techniques, instruments, and computer applications, a sharp distinction is made between the chemistry of organic (radical-)ions and analytical applications in biorganic chemistry and medicine. The emphasis is on the chemistry of organic (radical-)ions at the expense of inorganic, organometallic, and surface ion chemistry. Biochemistry and medicine are chosen because of their contemporary importance and because of the stupendous contributions of mass spectroscopy to these fields in the past two years. In the review of gas-phase organic ion chemistry, special attention is given to studies making significant contributions to the understanding of ion chemistry.

Burlingame, A. L.↗
DOE OSTI2024

Modulating Transition Metal Reactivity with Force

The reactivity and selectivity of a transition metal catalyst is intimately related to its ligand-sphere geometry, and, in many cases, the ideal ligand geometry for one step of a catalytic cycle is poorly matched to the ideal ligand geometry for another. For this reason, methods for reversibly modulating ligand geometry on the time scale of catalytic turnover or monomer enchainment are highly desirable. Mechanical force represents a heretofore untapped approach to modulate catalyst geometry and/or reactivity, with the potential to do so on the timescale of catalytic turnover or monomer enchainment. Macroscopic mechanical forces are large, directional and localized to an extent that differentiates them from other forms of energy input such as heat or light. Here, in this Concept, we describe our efforts to address the fundamental challenges associated with force-modulated transition metal catalysis by employing molecular force probe ligands comprising a stiff stilbene photoswitch tethered to rotationally flexible biaryl bisphosphine ligand. Our efforts to date include the modulation of catalytic activity through force-mediated ligand perturbations, quantification of the force-coupled ligand effects on the energetics of elementary organometallic transformations, and evaluation of the mechanisms of force transduction in these systems.

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

Mechanistic roles of metal- and ligand-protonated species in hydrogen evolution with [Cp*Rh] complexes

Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η 5 -pentamethylcyclopentadienyl (Cp*) ligands have recently been shown to undergo ligand-centered protonation by direct proton transfer from acids or tautomerization of metal hydrides, resulting in the generation of complexes bearing the uncommon η 4 -pentamethylcyclopentadiene (Cp*H) ligand. Here, time-resolved pulse radiolysis (PR) and stopped-flow spectroscopic studies have been applied to examine the kinetics and atomistic details involved in the elementary electron- and proton-transfer steps leading to complexes ligated by Cp*H, using Cp*Rh(bpy) as a molecular model (where bpy is 2,2′-bipyridyl). Stopped-flow measurements coupled with infrared and UV-visible detection reveal that the sole product of initial protonation of Cp*Rh(bpy) is [Cp*Rh(H)(bpy)] + , an elusive hydride complex that has been spectroscopically and kinetically characterized here. Tautomerization of the hydride leads to the clean formation of [(Cp*H)Rh(bpy)] + . Variable-temperature and isotopic labeling experiments further confirm this assignment, providing experimental activation parameters and mechanistic insight into metal-mediated hydride-to-proton tautomerism. Spectroscopic monitoring of the second proton transfer event reveals that both the hydride and related Cp*H complex can be involved in further reactivity, showing that [(Cp*H)Rh] is not necessarily an off-cycle intermediate, but, instead, depending on the strength of the acid used to drive catalysis, an active participant in hydrogen evolution. Identification of the mechanistic roles of the protonated intermediates in the catalysis studied here could inform design of optimized catalytic systems supported by noninnocent cyclopentadienyl-type ligands.

08 HYDROGEN↗
DOE OSTI2024

Silicon Nitride Surface Enabled Propane Dehydrogenation Catalyzed by Supported Organozirconium

Mesoporous silicon nitride (Si 3 N 4 ) is a nontraditional support for the chemisorption of organometallic complexes with the potential for enhancing catalytic activity through features such as the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor strength, and metal–ligand orbital overlap. In this report tetrabenzyl zirconium (ZrBn 4 ) was chemisorbed on Si 3 N 4 , and the resulting supported organometallic species was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear Polarization-enhanced Solid State Nuclear Magnetic Resonance (DNP-SSNMR), and X-ray Absorption Spectroscopy (XAS). Based on the hypothesis that the nitride might enable facile heterolytic C–H bond activation along the Zr–N bond, this material was found to be a highly active (1.53 mol propene mol Zr –1 h –1 at 450 °C) and selective (99% to propylene) catalyst for propane dehydrogenation. In contrast, the homologous silica supported complex exhibited negligible activity under these conditions.

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

Supported Organochromium Ethylene Oligomerization Enabled by Surface Lithiation

Here, in this work, supported organochromium ethylene polymerization catalysts have been tuned to mediate ethylene oligomerization via surface lithiation, which provides a generalizable protocol to control stereoelectronics and redox states of surface organometallic active sites. The homoleptic chromium(IV) alkyl complex Cr(CH 2 SiMe 3 ) 4 was grafted on high-surface-area anatase titania (TiO 2 ) nanoparticles as well as on silica to produce Cr/TiO 2 and Cr/SiO 2 , respectively. Treatment of these materials with excess n-butyllithium led to the reduced chromium complexes Cr/Li x TiO 2 and Cr/Li/SiO 2 , each of which still retains one hydrocarbyl ligand on chromium. A set of heterogeneous complexes were studied by electron paramagnetic resonance and X-ray absorption spectroscopy, which indicate a reduction in the oxidation state of the major chromium species to Cr II upon lithiation. Cr/Li x TiO 2 converts ethylene to hexenes with a high selectivity (>80%), which was persistent over 10 days at 80 °C, achieving >950 turnovers. The exclusive formation of C 4 and C 6 olefins, preferring the trimerization product, without a statistical (Flory–Schulz) distribution is characteristic of the oxidative cyclization oligomerization mechanism rather than the traditional Cossee–Arlman mechanism, whereas Cr/Li/SiO 2 produced a mixture of trimerization and polymerization products, suggesting site heterogeneity in the silica-based material. On the other hand, the unreduced chromium(IV) materials as well as low lithium-containing Cr/Li x TiO 2 (x < 0.16) exclusively produced ultrahigh molecular weight polyethylene, determined by differential scanning calorimetry and gel permeation chromatography analysis, likely formed via a linear-insertion mechanism, with a crossover from the polymerization to oligomerization regime observed at ~16% Li intercalation.

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

Ammonia Synthesis by a Supported Iron-Lithium Hydride Precatalyst: Silicon Nitride Support Enabled Synthesis and Nitrogen Reservoir Dynamics

Amorphous silicon nitride (Si 3 N 4 ) is an unconventional support for the chemisorption of organometallic complexes and offers potential improvements in active site stability and reactivity through enhanced metal-nitrogen covalency and orbital overlap in bonding interactions with the nitride framework. Here, we show that silicon nitride-supported iron mesityl complexes display divergent reactivity compared to their silica-supported homologues, resisting metallic particle formation under reducing pretreatment conditions (exposure to excess organolithium reagents) and maintaining active iron/lithium speciation under ammonia synthesis conditions that is absent on the oxide support. When the organometallic iron complex on silicon nitride is exposed to excess n-butyllithium, iron remains isolated, catalyzing the conversion of butyllithium to lithium hydride, resulting in a divalent iron site in a polyhydride environment. In contrast, the silica-supported complex is converted to reduced iron clusters without forming persistent isolated hydrides. These structural differences lead to markedly different catalytic behaviors under ammonia synthesis conditions. The Li/Fe/Si 3 N 4 catalyst is highly active (7.5 mol NH 3 /mol Fe/h at 300 °C, 10 bar, or 46 mol NH 3 /mol Fe/h at 400 °C, 10 bar), while both the silica-supported analog and the nonlithiated Si 3 N 4 -supported species are inactive. Notably, this activity is enhanced relative to previously reported iron-lithium hydride composite catalysts (0.43–4.1 mol NH 3 /mol Fe/h at 300 °C, 10 bar) and relative to the industrial benchmark promoted iron catalyst KM1 (3.0 mol NH 3 /mol Fe/h at 400 °C, 10 bar). The catalyst activation and LiH/LiNH x nitrogen reservoir dynamics for Li/Fe/Si 3 N 4 are studied by X-ray Absorption, Mössbauer, and in situ DRIFT spectroscopies and isotopic exchange kinetics.

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

The Exceptional Diversity of Homoleptic Uranium–Methyl Complexes

Homoleptic σ-bonded uranium–alkyl complexes have been a synthetic target since the Manhattan Project. The current study describes the synthesis and characterization of several unprecedented uranium–methyl complexes. Amongst these complexes, the first example of a homoleptic uranium–alkyl dimer, [Li(THF) 4 ] 2 [U 2 (CH 3 ) 10 ], as well as a seven-coordinate uranium–methyl monomer, {Li(OEt 2 )Li(OEt 2 ) 2 UMe 7 Li} n were both crystallographically identified. We report the diversity of complexes reported herein provides critical insight into the structural diversity, electronic structure and bonding in uranium–alkyl chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗