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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 OSTI2024

Advances in electrosynthesis for a greener chemical industry

As nations unite to curb anthropogenic greenhouse gas emissions, the decarbonization of the chemical industry has been propelled to the forefront of scientific research. Renewable electricity will play a central role in this effort. In addition to powering chemical plants and allowing for the sustainable production of heat to drive thermocatalytic processes, renewable electricity also provides the chemical industry with opportunities to engage in the sustainability revolution and broadly reduce its environmental footprint through breakthrough innovations in direct electrochemical transformations. The electrification of chemical synthesis—electrosynthesis—is a promising route to promote sustainability without compromising economic competitiveness. Electrosynthesis uses electrons both as an energy source to drive reactions and as a green reagent for chemical reductions and oxidations under ambient conditions. Therefore, it holds tremendous potential (pun intended) to increase selectivity to desired products, open green reaction pathways for challenging transformations (e.g., Birch reduction, epoxidations, coupling reactions), and reduce chemical waste.

08 HYDROGEN↗
NASA NTRS1977

On the formation and destruction of chlorine negative ions in the D region

We have investigated the possible reactions of chlorine atoms, chlorine monoxide, and hydrogen chloride with D region negative ions. The mesospheric concentrations of the neutral chlorine gases have been predicted with a diurnally varying one-dimensional model of the upper atmosphere. Despite the low abundances of chlorine compounds in air their high reactivity leads to the formation of substantial quantities of clorine negative ions at high altitudes. The concentration of chlorine ions is limited in daylight by rapid reactions with oxygen and hydrogen atoms and at night by the competitive production of other stable ions. The presence of chlorine negative ions in the upper atmosphere is consistent with in situ mass spectrometer observations of charged species. The abundance of chlorinated ions in the D region may be correlated with mesospheric nitric oxide and water vapor concentrations.

Turco, R. P.↗
NASA NTRS2014

Towards Co-evolution of Membranes and Metabolism

Conceptually, the most robust way to explain how primitive cell-like structures acquired and increased their capabilities is on the basis of Darwinian evolution. A population of protocells containing material that produced more environmentally fit progeny would increase in time at the expense of other protocells. In this scenario, protocellular boundaries were inextricably connected to the metabolism they encapsulated: to be inheritable, early metabolism must have led to an increased rate of growth and division of vesicles and, similarly, transport through vesicle boundaries must have supported the evolution of metabolism. Everything that could not be delivered from the environment had to be produced and retained inside protocells. Despite their importance to the understanding of the origin of life, only a few cases of coupling between metabolism and membrane-related processes have been identified so far. For example, reactions inside fatty-acid vesicles have been linked to their competitive growth and division, and mechanisms by which membrane permeability might have coupled to information polymers have been proposed and explained. Most recently, it has been shown that a dipeptide inside fatty-acid vesicles catalyzes the formation of another dipeptide that binds to vesicle walls and, by doing so, promotes their growth at the expense of other vesicles, thus demonstrating evolutionary advantage of small, membrane-bound peptides. It has been shown that the appearance of phospholipids imparted selective advantage to protocells bound by phospholipid-containing membranes, eventually driving fatty-acid vesicles to extinction. Phospholipid membranes, however, are nearly impermeable to charged species. Yet, the ability to transport ions across membranes was vital for regulating cellular volume, pH homeostasis, generating energy and sensing the environment. To account for this, evolutionary scenarios for the emergence of simple ion channels, protein structures surrounding water-filled pores in the membrane that facilitate ion transport, have been developed. We will review recent progress in experimental and theoretical studies on coupling properties of membranes to metabolism, with the focus on how they impose constraints on scenarios for the origin of life, and discuss how these studies form the basis for future work on this topic.

metabolism↗
DOE OSTI2024

Quantum dynamics of positron-hydrogen scattering and three-body bound state formation with an assisting laser field: predictions of a reduced-dimensionality model

Abstract We investigate the quantum dynamics of target excitation and positronium formation in the positron-hydrogen atom scattering without and with an external assisting laser field within a reduced-dimensional quantum model. Strong interference fringes between the incident and reflected positron wave packets are observed in the reaction region. We further investigate the critical behavior of transition probabilities near the channel-opening thresholds for hydrogen excitation and positronium formation and find a strong competition between channels with similar threshold energies, but different parities. The transmission ratios of the incident positron in different reaction channels are calculated, and it is shown that only positronium formation in the ground state prefers forward scattering. Our simulation of the positron-hydrogen scattering with an assisting laser field indicates that the three-particle bound states can be formed during the collisions due to the photon emission induced by the external laser field.

Optics↗
DOE OSTI2020

Mapping Competitive Reduction upon Charging in LiNi 0.8 Co 0.15 Al 0.05 O 2 Primary Particles

Side reactions involving surface reduction play a critical role in the failure of LiNi 0.8 Co 0.15 Al 0.05 O 2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscopic consequences are known, the underlying nanoscopic mechanisms are not fully elucidated. By coupling X-ray spectroscopy with several X-ray microscopy modalities, we have spatially resolved the extent of Ni oxidation at several states of charge and uncovered heterogeneity that is hidden when considering ensemble measurements alone. The use of morphologically controlled particles enabled high-resolution imaging of these materials, uncovering gradients of Ni oxidation states within individual primary particles. At high states of charge, these gradients revealed regions of possible oxygen deficiency extending deeper into the particle than previously observed. Surface-sensitive X-ray coupled scanning tunneling microscopy allows oxidation states to be measured at the material's surface, showing predominantly Ni II in the first atomic layer and mixtures of Ni II with Ni III /Ni IV already appearing 1.5 nm into the particle. These results reveal the subtle interplay between irreversible surface transformations and the bulk reactions that ultimately define function, which will refine strategies of surface passivation that are key to overcoming current performance limitations.

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

Tuning Structural and Electronic Configuration of FeN 4 via External S for Enhanced Oxygen Reduction Reaction

The Fe–N–C material represents an attractive oxygen reduction reaction electrocatalyst, and the FeN 4 moiety has been identified as a very competitive catalytic active site. Fine tuning of the coordination structure of FeN 4 has an essential impact on the catalytic performance. Herein, we construct a sulfur‐modified Fe–N–C catalyst with controllable local coordination environment, where the Fe is coordinated with four in‐plane N and an axial external S. The external S atom affects not only the electron distribution but also the spin state of Fe in the FeN 4 active site. The appearance of higher valence states and spin states for Fe demonstrates the increase in unpaired electrons. With the above characteristics, the adsorption and desorption of the reactants at FeN 4 active sites are optimized, thus promoting the oxygen reduction reaction activity. This work explores the key point in electronic configuration and coordination environment tuning of FeN 4 through S doping and provides new insight into the construction of M–N–C‐based oxygen reduction reaction catalysts.

25 ENERGY STORAGE↗
DOE OSTI2020

Catalytic consequences of hydrogen addition events and solvent-adsorbate interactions during guaiacol-H 2 reactions at the H 2 O-Ru(0 0 0 1) interface

Catalytic reactions of biomass-derived phenolics and H 2 occur on transition metal surfaces via competitive C–O cleavage and ring saturation pathways, with both requiring multiple hydrogen addition events before forming their respective rate limiting transition states. These events are markedly affected by solvent chemical identity, with polar protic solvents ionizing hydrogen adatoms (H*) to interfacial protons (H + ) and opening up new catalytic routes. Here, we establish the reaction coordinate space for guaiacol-H 2 reactions on Ru(0 0 0 1) using density functional theory and describe the atomic-scale effect of a polar protic solvent, H 2 O. Coupled H + and H* attack leads to quasi-equilibrated enol and keto intermediates as the precursors for C–O cleavage and ring saturation, respectively. For C–O cleavage, H 2 O solvent enables a lower energy pathway via concomitant transfer of the hydroxyl H + to the methoxy oxygen during C–OCH 3 cleavage, forming a charge separated [Ru(s)–(C 6 H 5 O – )…(H + )…OCH 3 ] transition state and reducing the barrier by up to 0.8 eV as compared to unassisted C–OCH 3 cleavage. For ring saturation, H* attack onto an unsaturated meta carbon is rate limiting with no direct solvent participation, suggesting that protic polar solvents selectively promote the C–O cleavage pathway. Taken together, we show that activating guaiacol for either C–O bond cleavage or ring saturation product formation depends on the reactive hydrogen identity (H* or H + ), enol/keto isomerization equilibrium, and accessibility of the proton assisted Car–OCH 3 cleavage transition state. Here, all such factors are tunable via changes to the solvent or metal identity.

09 BIOMASS FUELS↗
DOE OSTI2020

Covalency competition dominates the water oxidation structure–activity relationship on spinel oxides

Spinel oxides have attracted growing interest over the years for catalysing the oxygen evolution reaction (OER) due to their efficiency and cost-effectiveness, but fundamental understanding of their structure–property relationships remains elusive. Here we demonstrate that the OER activity on spinel oxides is intrinsically dominated by the covalency competition between tetrahedral and octahedral sites. The competition fabricates an asymmetric M$_T-O-M_O$ backbone where the bond with weaker metal–oxygen covalency determines the exposure of cation sites and therefore the activity. Driven by this finding, a dataset with more than 300 spinel oxides is computed and used to train a machine-learning model for screening the covalency competition in spinel oxides, with a mean absolute error of 0.05 eV. [Mn]$_T$[Al$_{0.5}$Mn$_{1.5}$]OO$_4$ is predicted to be a highly active OER catalyst and subsequent experimental results confirm its superior activity. This work sets mechanistic principles of spinel oxides for water oxidation, which may be extendable to other applications.

36 MATERIALS SCIENCE↗
NASA NTRS1996

An Overview on Aerospatiale Magnetic Bearing Products for Spacecraft Attitude Control and for Industry

Aerospatiale magnetic bearings are based on the use of permanent magnets and on the control of the rotor around a zero force equilibrium point. The present developments of magnetic bearing wheels for space applications focus on the versatility of a basic design which leads to a family of reaction and momentum wheels with tailored torque and kinetic momentum, leading to competitive mass and cost. The present industrial applications concern kinetic energy accumulators, medical x-ray rotating devices, avionics equipment, cryotechnic compressors and vacuum pumps.

Samuel, Alain↗
DOE OSTI2021

Competitive Exclusion and Metabolic Dependency among Microorganisms Structure the Cellulose Economy of an Agricultural Soil

Microorganisms that degrade cellulose utilize extracellular reactions that yield free by-products which can promote interactions with noncellulolytic organisms. We hypothesized that these interactions determine the ecological and physiological traits governing the fate of cellulosic carbon (C) in soil. We performed comparative genomics with genome bins from a shotgun metagenomic-stable isotope probing experiment to characterize the attributes of cellulolytic and noncellulolytic taxa accessing 13 C from cellulose. We hypothesized that cellulolytic taxa would exhibit competitive traits that limit access, while noncellulolytic taxa would display greater metabolic dependency, such as signatures of adaptive gene loss. We tested our hypotheses by evaluating genomic traits indicative of competitive exclusion or metabolic dependency, such as antibiotic production, growth rate, surface attachment, biomass degrading potential, and auxotrophy. The most 13 C-enriched taxa were cellulolytic Cellvibrio (Gammaproteobacteria) and Chaetomium (Ascomycota), which exhibited a strategy of self-sufficiency (prototrophy), rapid growth, and competitive exclusion via antibiotic production. Auxotrophy was more prevalent in cellulolytic Actinobacteria than in cellulolytic Proteobacteria, demonstrating differences in dependency among cellulose degraders. Noncellulolytic taxa that accessed 13 C from cellulose (Planctomycetales, Verrucomicrobia, and Vampirovibrionales) were also more dependent, as indicated by patterns of auxotrophy and 13 C labeling (i.e., partial labeling or labeling at later stages). Major 13 C-labeled cellulolytic microbes (e.g., Sorangium, Actinomycetales, Rhizobiales, and Caulobacteraceae) possessed adaptations for surface colonization (e.g., gliding motility, hyphae, attachment structures) signifying the importance of surface ecology in decomposing particulate organic matter. Our results demonstrated that access to cellulosic C was accompanied by ecological trade-offs characterized by differing degrees of metabolic dependency and competitive exclusion.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2018

Three Stage Cool Flame Droplet Burning Behavior of n-Alkane Droplets at Elevated Pressure Conditions: Hot, Warm and Cool Flame

Transient, isolated n-alkane droplet combustion is simulated at elevated pressure for helium-diluent substituted-air mixtures. We report the presence of unique quasi-steady, three-stage burning behavior of large sphero-symmetric n-alkane droplets at these elevated pressures and helium substituted ambient fractions. Upon initiation of reaction, hot-flame diffusive burning of large droplets is initiated that radiatively extinguishes to establish cool flame burning conditions in nitrogen/oxygen “air” at atmospheric and elevated pressures. However, at elevated pressure and moderate helium substitution for nitrogen ( X He > 20%), the initiated cool flame burning proceeds through two distinct, quasi-steady-state, cool flame burning conditions. The classical “Hot flame ” ( ∼1500 K) radiatively extinguishes into a “Warm flame ” burning mode at a moderate maximum reaction zone temperature ( ∼ 970 K), followed by a transition to a lower temperature ( ∼765 K), quasi-steady “Cool flame ” burning condition. The reaction zone (“flame”) temperatures are associated with distinctly different yields in intermediate reaction products within the reaction zones and surrounding near-field, and the flame-standoff ratios characterizing each burning mode progressively decrease. The presence of all three stages first appears with helium substitution near 20%, and the duration of each stage is observed to be strongly dependent on helium substitutions level between 20–60%. For helium substitution greater than 60%, the hot flame extinction is followed by only the lower temperature cool flame burning mode. In addition to the strong coupling between the diffusive loss of both energy and species and the slowly evolving degenerate branching in the low and negative temperature coefficient (NTC) kinetic regimes, the competition between the low-temperature chain branching and intermediate-temperature chain termination reactions control the “Warm” and “Cool ” flame quasi-steady conditions and transitioning dynamics.

Droplet Combustion↗
DOE OSTI2023

Aldehyde and Ketone Hydroboration Mediated by a Heterogeneous Single–Site Molybdenum–Dioxo Catalyst: Scope and Mechanistic Implications

Efficient hydroboration of aldehydes and ketones is demonstrated using a single-site MoO 2 catalyst supported on activated carbon. Under mild conditions with low catalytic loadings, the reaction exhibits chemoselectivity towards carbonyl reduction over halides, alkene, alkyne, nitrile, and ester groups, affording high yields of desired products. Furthermore, competition studies between aldehyde and ketone reduction using HBpin and HBcat indicate that HBpin preferably functionalizes aldehydes, while HBcat can functionalize either substrate under specific conditions. Mechanistic studies suggest that the reaction proceeds via the initial formation of a molybdenum-hydride species upon B–H activation and subsequent molybdenum-alkoxide species upon carbonyl activation by the Mo center. The experimental activation energy of 14.3 kcal/mol alignssatisfactorily with the DFT computed ΔH ≠ of 18.7 kcal/mol, further supporting the proposed mechanism. Combined experimental/computational analyses reveal that excess HBpin can possibly deactivate the catalyst. The presence of excess benzaldehyde efficiently mitigates deactivation by HBpin, providing significantly higher catalyst recyclability. Altogether, this non-toxic, air- and moisture-stable, active, and selective catalyst demonstrates significant potential for green processes.

08 HYDROGEN↗
DOE OSTI2023

General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System

The pH dependence of proton-coupled electron transfer (PCET) reactions, which are critical to many chemical and biological processes, is a powerful probe for elucidating their fundamental mechanisms. Herein, a general, multichannel kinetic model is introduced to describe the pH dependence of both homogeneous and electrochemical PCET reactions. According to this model, a weak pH dependence can arise from the competition among multiple sequential and concerted PCET channels involving different forms of the redox species, such as protonated and deprotonated forms, as well as different proton donors and acceptors. The contribution of each channel is influenced by the relative populations of the reactant species, which often depend strongly on pH, leading to complex pH dependence of PCET apparent rate constants. This model is used to explain the origins of the experimentally observed weak pH dependence of the electrochemical PCET apparent rate constant for a ruthenium-based water oxidation catalyst attached to a tin-doped In2O3 (ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. Furthermore, this work highlights the importance of considering multiple competing channels simultaneously for PCET processes.

Catalysts↗
DOE OSTI2020

Competitive Adsorption of Ionic Liquids Versus Friction Modifier and Anti-Wear Additive at Solid/Lubricant Interface—Speciation with Vibrational Sum Frequency Generation Spectroscopy

A modern lubricant contains various additives with different functionalities and the interactions or reactions between these additives could induce synergistic or antagonistic effects in tribological performance. In this study, sum frequency generation (SFG) spectroscopy was used to investigate competitive adsorption of lubricant additives at a solid/base oil interface. A silica substrate was used as a model solid surface. The lubricant additives studied here included two oil-soluble ionic liquids (ILs, [N888H][DEHP] and [P8888][DEHP]), an antiwear additive (secondary ZDDP), an organic friction modifier (OFM), and a dispersant (PIBSI). Our results showed that for mixtures of ZDDP and IL in a base oil (PAO4), the silica surface is dominated by the IL molecules. In the cases of base oils containing OFM and IL, the silica/lubricant interface is dominated by OFM over [N888H][DEHP], while it is preferentially occupied by [P8888][DEHP] over OFM. The presence of PIBSI in the mixture of PAO4 and IL leads to the formation of a mixed surface layer at the silica surface with PIBSI as a major component. The SFG results in this investigation provide fundamental insights that are helpful to design the formulation of new lubricant additives of desired properties.

25 ENERGY STORAGE↗
DOE OSTI2021

Mathematical modeling of novel porous transport layer architectures for proton exchange membrane electrolysis cells

Thin foil based porous transport layers (PTLs) that contain highly structured pore arrays have shown promise as anode PTLs in proton exchange membrane electrolysis cells. These novel PTLs, fabricated with advanced manufacturing techniques, produce thin, tunable, multifunctional layers with reduced flow and interfacial resistances and high thermal and electric conductivities. To further optimize their design, it is important to understand their fundamental impact on the transport of protons, electrons, and liquid/vapor mixtures in the electrode. In this work, we develop a two-dimensional multiphysics model to simulate the coupled electrochemistry and multiphase transport in an electrolysis cell operated with the novel PTL architecture. The results show that larger pores improve access of water to the anode catalyst layer, which is beneficial for both the oxygen evolution reaction and membrane hydration. Larger pore sizes also improve oxygen gas transport from the catalyst layer, because generated oxygen gas is forced to travel in-plane through the anode catalyst layer until it reaches a pore opening that is connected to a channel. The discussed results confirm that the proposed thin foil based PTLs are fundamentally different from conventional PTLs, such as felts or layered meshes. The model developed in this work also provides generalizable insight into fundamental PEMEC phenomena, such as the competition between liquid and gas phase transport, membrane hydration and water management, and nonuniform electrochemical reactions, which are processes relevant to all PEMEC designs.

25 ENERGY STORAGE↗
DOE OSTI2024

Photocatalytic Semi‐Hydrogenation of Acetylene to Polymer‐Grade Ethylene with Molecular and Metal–Organic Framework Cobaloximes

Abstract The semi‐hydrogenation of acetylene in ethylene‐rich gas streams is a high‐priority industrial chemical reaction for producing polymer‐grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H 2 consumption, possess relatively low selectivity, and use a noble metal catalyst. Light‐powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation, but are ineffective. Here an efficient, >99.9% selective, visible‐light powered, catalytic conversion of acetylene to ethylene is reported. The catalyst is a homogeneous molecular cobaloxime that operates in tandem with a photosensitizer at room temperature and bypasses the use of non‐environmentally friendly and flammable H 2 gas feed. The reaction proceeds through a cobalt‐hydride intermediate with ≈100% conversion of acetylene under competitive (ethylene co‐feed) conditions after only 50 min, and with no evolution of H 2 or over‐hydrogenation to ethane. The cobaloxime is further incorporated as a linker in a metal–organic framework; the result is a heterogeneous catalyst for the conversion of acetylene under competitive (ethylene co‐feed) conditions that can be recycled up to six times and remains catalytically active for 48 h, before significant loss of performance is observed.

Stone, Aaron E. B. S.↗
DOE OSTI2023

Elucidating a dissolution–deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO 2 batteries

Aqueous Zn/MnO 2 batteries with their environmental sustainability and competitive cost, are becoming a promising, safe alternative for grid-scale electrochemical energy storage. Here, presented as a promising design principle to deliver a higher theoretical capacity, this work offers fundamental understanding of the dissolution–deposition mechanism of Zn/β-MnO 2 . A multimodal synchrotron characterization approach including three operando X-ray techniques (powder diffraction, absorption spectroscopy, and fluorescence microscopy) is coupled with elementally resolved synchrotron X-ray nano-tomography. Together they provide a direct correlation between structural evolution, reaction chemistry, and 3D morphological changes. Operando synchrotron X-ray diffraction and spectroscopy show a crystalline-to-amorphous phase transition. Quantitative modeling of the operando data by Rietveld refinement for X-ray diffraction and multivariate curve resolution (MCR) for X-ray absorption spectroscopy are used in a complementary fashion to track the structural and chemical transitions of both the long-range (crystalline phases) and short-range (including amorphous phases) ordering upon cycling. Scanning X-ray microscopy and full-field nano-tomography visualizes the morphology of electrodes at different electrochemical states with elemental sensitivity to spatially resolve the formation of the Zn- and Mn-containing phases. Overall, this work critically indicates that for Zn/MnO 2 aqueous batteries, the reaction pathways involving Zn–Mn complex formation upon cycling become independent of the polymorphs of the initial electrode and sheds light on the interplay among structural, chemical, and morphological evolution for electrochemically driven phase transitions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Insight into the Competitive Adsorption Behavior of Polymer Chains in Silica Nanopores by Small-Angle Neutron Scattering

Processive hydrogenolysis catalysts, in which a metal nanoparticle (e.g., Pt) embedded at the bottom of a cylindrical silica nanopore can repeatedly cleave polymer chains and produce value-added hydrocarbon products, offer a potential solution for billions of tons of waste plastics. As the chain stays longer near the Pt catalysts, it would have a higher chance of getting cut, and therefore the molecular weight distribution of the product could be affected by the adsorption behavior of virgin chains (long polymers) versus cleaved chains (short polymers) into the nanopores. Further, this work reports a model study to understand the competitive adsorption behavior of the two different molecular weight polymers that are mixed, mimicking the reaction medium in the intermediate stage of the catalytic reaction. This study employs small-angle neutron scattering (SANS), which takes advantage of contrast differences between hydrogenous and deuterated polystyrenes to experimentally observe the relative composition of the two polymers in the silica nanopores. Our results reveal preferential adsorption of longer chains in the silica nanopores, which is consistent with the theoretical prediction in the literature for the case of the enthalpic attraction between polymers and pore walls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗