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Photooxidation of Polyolefins to Produce Materials with In-Chain Ketones and Improved Materials Properties

Herein, we report a selective photooxidation of commodity postconsumer polyolefins to produce polymers with in-chain ketones. The reaction does not involve the use of catalyst, metals, or expensive oxidants, and selectively introduces ketone functional groups. Under mild and operationally simple conditions, yields up to 1.23 mol % of in-chain ketones were achieved. Installation of in-chain ketones resulted in materials with improved adhesion of the materials and miscibility of mixed plastics relative to the unfunctionalized plastics. The introduction of ketone groups into the polymer backbone allows these materials to react with diamines, forming dynamic covalent polyolefin networks. This strategy allows for the upcycling of mixed plastic waste into reprocessable materials with enhanced performance properties compared to polyolefin blends. Mechanistic studies support the involvement of photoexcited nitroaromatics in consecutive hydrogen and oxygen atom transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

New procedure for evaluation of U(3) coupling and recoupling coefficients

A simple method to calculate Wigner coupling coefficients and Racah recoupling coefficients for U(3) in two group–subgroup chains is presented. While the canonical U(3) coupling and recoupling coefficients are applicable to any system that respects U(3) symmetry, the U(3) coupling coefficients are more specific to nuclear structure studies. This new procedure precludes the use of binomial coefficients and alternating sums which were used in the 1973 formulation of Draayer and Akiyama, and in so doing provides a faster and more accurate determination of any and all required results. The resolution of the outer multiplicity is based on the null space concept of the U(3) generators proposed by Alex et al., whereas the inner multiplicity in the angular momentum subgroup chain is obtained from the dimension of the null space of the SO(3) raising operator. It is anticipated that a C++ library will ultimately be available for determining generic coupling and recoupling coefficients associated with both the canonical and the physical group–subgroup chains of U(3).

Cross-Coupling Reaction

Integrated Systems-to-Atoms (S2A) Framework for Designing Resilient and Efficient Hydrogen Infrastructure Solutions

The success of a future clean hydrogen infrastructure will depend on technology performance, operating conditions, and system configuration, which will be integrated to meet specific end-use requirements. We introduce a Systems-to-Atoms framework to cosimulate material, device, and system design for clean hydrogen storage and transport. Here we present a demonstration scenario in which hydrogen is distributed using a liquid organic hydrogen carrier to 700 bar refueling stations. Cross-scale analysis on hydrogen release at the refueling station reveals that while a high reaction pressure (up to 100 bar) may not enhance the catalyst performance, it can lead to system-level cost savings (up to 5% of total refueling station cost) due to savings in downstream gas compression. Further, a typically low-performing dehydrogenation catalyst material (e.g., copper) may be preferred over a high-performing catalyst (e.g., palladium) at different operating conditions when considering overall system affordability and supply chain resilience.

08 HYDROGEN

Supramolecular Metal‐Organic Framework Electrocatalysts With Hydration‐Adaptive Gallery Expansion and Linker‐Mediated Distal Ni‐Co Cooperation Enable Framework‐Retentive Oxygen Evolution

Atomic‑level tailoring of electronic communication between spatially separated metal sites offers a route to accelerate multielectron electrocatalysis. We report Ni-TPTC, Co-TPTC, and heterobimetallic Ni-Co-TPTC supramolecular metal-organic frameworks (SMOFs) for the oxygen evolution reaction (OER) built from a terphenyl‑tetracarboxylate (TPTC) linker. Single-crystal X-ray diffraction of heterobimetallic Ni–Co–TPTC reveals trans-bis-aqua octahedral chains assembled into a π-stacked, hydrogen-bonded lattice and confirms retention of the parent architecture, while powder X-ray diffraction supports an isostructural Co analog. In 1.0 M KOH, Ni-Co-TPTC reaches 20 mA cm −2 at 350 mV and maintains operation at ∼60 mA cm −2 for 45 h with modest decay of the initial current. Time‑dependent ex situ diffraction shows dominant framework reflections with low‑angle shifts consistent with gallery dilation (d‑spacing ∼7.7 → ∼9.2 Å) during early operation, while Co K‑edge X‑ray absorption and microscopy reveal Co‑rich oxide/oxyhydroxide‑like domains at longer times that correlate with decay. X‑ray photoelectron spectroscopy, quantified by the Remote Binding‑Energy Differential, tracks composition‑dependent Ni-Co polarization, and DFT free‑energy analysis suggests that a model Ni-Co environment lowers the Co‑centered potential‑limiting step by ∼0.24 eV relative to the Co‑only framework. Furthermore, these results suggest that framework‑retentive expansion and distal Ni-Co coupling can drive OER activity before gradual deligation and oxide formation mark longer‑time degradation.

Supramolecular metal-organic frameworks (SMOFs)

Solar Heat for Industrial Processes: Integration with Chemical Reactors

The integration of solar thermal systems with chemical reactors has been proposed as part of a larger effort to develop and deploy solar heat for industrial processes (SHIP) technologies. A strong motivation for SHIP processes and technologies is the potential for high thermal efficiency coupled with low-cost thermal energy storage (TES) which can enable commercial deployment of such systems. While there are different ways to categorize SHIP technologies, one important such distinction is between directly irradiated systems and indirect off-sun process driven by a SHIP system. While directly irradiated systems can provide high thermal efficiencies and high fluxes, they usually require complex engineering solutions due to the need for redesigning the established processes and unit operations. In most cases, it is also more challenging to couple such a process to a TES system, losing some of the benefits of SHIP. On the other hand, using a SHIP system to drive an industrial process off-sun can allow better integration with existing process chains, easier TES capabilities, and potential for more applications fitting a specific SHIP technology. However, the integration of SHIP systems with the industrial processes is not fully explored in detail, especially in the case of high-temperature processes such as reforming, cracking, cement manufacturing, and iron/steelmaking. Many of these systems require heating fluxes of >50 kW/m^2, supplied via combustion of hydrocarbons in a fire box and benefitting from radiative heat transfer between the flue gases and the reaction zones. As such, using SHIP systems for such processes is more complex than providing the same thermal input in the form of a heat transfer medium (HTM) entering the reactor, kiln, or furnace. Moreover, in case convective heat transfer using SHIP is envisioned, for example using supercritical CO2 as the HTM from a particle receiver, the thermal integration might be more challenging than initially envisioned: lower heat transfer coefficients and limited approach temperature might require large flow rates, causing a mismatch between the process thermal requirements and the thermal capacity of the SHIP system. In addition, even if the heat exchange between SHIP and reactor is effective, there is still a cold leg HTM at the reaction temperature or slightly below it. Chemical plants usually include a set of heat exchangers, heat recovery steam generators, and even power generation units - in a tightly integrated design - to recover the flue gases which are eventually vented. With SHIP systems mostly operating on a closed HTM loop, bottoming the cold leg is crucial. In this talk, we will present different modeling results for a variety of syngas production reactions, using catalytic and chemical looping processes, and discuss some of the challenges and design considerations for off-sun chemical reactors using SHIP systems.

14 SOLAR ENERGY

Discovery of new isotopes in the fragmentation of 82 Se and insights into their production

The production cross sections of neutron-rich nuclei for elements just above 60 Ca were measured at the Facility for Rare Isotope Beams (FRIB). Four previously unobserved isotopes ( 63 Sc, 65,66 Ti, and 68 V) were produced, separated, and identified for the first time using the Advanced Rare Isotope Separator (ARIS). One event was found to be consistent with 61 Ca . The new isotopes were created through the interaction of an 82 Se beam with a carbon target at an energy of 228 MeV/𝑢 and a primary beam current of 1.07 p⁢µ⁢A. The event-by-event particle identification of the mass number (𝐴), atomic number (𝑍), and ionic charge state (𝑞) for the reaction products was achieved by combining measurements of energy loss, time of flight, magnetic rigidity, and total kinetic energy. This successful search for new isotopes, conducted at the beginning of FRIB's third year of operation, highlights the facility's discovery potential, which will continue to grow as the beam current increases. The production cross sections were analyzed in the context of the newly developed Δ⁢𝐵⁢𝐸 systematics that provides trends in neutron-rich regions and increased sensitivity to nuclear binding, an important nuclear structure observable. Furthermore, the new systematics addresses gaps in 𝑄 𝑔 -based methods commonly used to interpret the production cross sections of light neutron-rich elements, and provides an efficient empirical approach to describe cross-section trends across isotopic chains. Good agreement with the measured data was obtained when the Δ⁢𝐵⁢𝐸 systematics and abrasion-ablation calculations were performed using the Hartree-Fock-Bogoliubov (HFB-22) mass table.

59 ≤ A ≤ 89

Optimizing Nonaqueous Sodium–Polysulfide Redox-Flow Batteries: The Role of Solvation Effects with Glyme Solvents

Nonaqueous redox-flow batteries (NARFBs) that use economical alkali metals and the corresponding metal polysulfides are highly attractive for grid-scale energy storage. Although sodium–sulfur systems have been recognized as promising candidates and have been the focus of many studies due to their high earth abundance and energy density, an understanding of the role of the solvation chemistry of commonly used glyme solvents is missing. Herein, we report a systematic investigation into the solvation effects of glyme-based Na-S electrolytes through comprehensive physiochemical experiments and Density Functional Theory (DFT) simulations. Our findings revealed, on one hand, that an optimal coordination strength between glymes and Na + could maintain a relatively smooth Na + diffusion. On the other hand, glyme solvents with extended chain lengths shift the reduction potential of S 8 2– negatively to elevate the formation barrier of undesirable short-chain polysulfides (S n 2– , n ≤ 4) that have high membrane permeability. This solvation phenomenon not only mitigates capacity fading but also extends the operational longevity of the Na-S NARFBs. In conclusion, the results underscore the critical roles of balanced solvent–cation interactions and controlled redox potentials in improving the stability and efficiency of Na-S NARFB systems, marking a significant advancement in the development of sustainable energy storage solutions.

25 ENERGY STORAGE

Understanding and Mitigating Stickiness in Biochar Produced through Acid Hydrolysis and Dehydration

Levulinic acid is a platform chemical with significant potential for conversion into a wide range of biobased chemicals and fuels. A common process for producing levulinic acid from lignocellulosic feedstocks involves acid hydrolysis and dehydration (AHDH), where hexose polymers are hydrolyzed into monomeric sugars and subsequently dehydrated to levulinic acid and formic acid in the presence of dilute sulfuric acid. However, scaling the AHDH process is challenging because of the formation of byproducts such as sticky biochar, which accumulates in continuous-flow reactors, reducing effective reaction volume and increasing process downtime. This study investigates the effect of a chemical preconditioning step on mitigating sticky biochar formation. Woody biomass was preconditioned at 170 °C with 0.26 wt % sulfuric acid for 30 min, resulting in substantial removal of hemicellulose and acid-soluble lignin. AHDH of these preconditioned solids produced biochar that did not adhere to reactor surfaces. TGA analysis confirmed that the chemical preconditioning step minimized interactions between hemicellulose-derived degradation products and lignin side chains, reducing sticky char formation. Additionally, the study observed a 6% higher yield of organic acids from softwood species compared to hardwoods, with bark content shown to negatively impact yield. These findings suggest that targeted preconditioning of lignocellulosic biomass can enhance reactor operability and improve organic acid production efficiency in AHDH processes.

biopolymers

Harnessing ketones as hydrogen acceptors for atom-efficient upgrading of oxygenates to fuels over H/ZSM-5

Heterogeneous mixtures of bio-derived oxygenates are promising feedstocks for synthetic aviation fuel (SAF), but conversion strategies for one common component—short-chain (C 5–7 ) internal ketones—are lacking. Previous work has shown that cyclization of ketones over H/ZSM-5 is limited by its high productivity of light paraffins. We study 4-heptanone upgrading over H/ZSM-5 and show that aromatics and olefins can be formed at high carbon yield when operating at up to 90% conversion. The yield of desirable products is not impacted by the introduction of a recycle stream of the unconverted 4-heptanone and other products with similar boiling points. We hypothesize, based on first-principles calculations, that the higher olefin yield is driven by the ease of hydrogen transfer to unreacted ketones as opposed to hydrogenating olefin products. We demonstrate how this ease of hydrogen transfer to ketones can be leveraged to enhance olefin selectivity in the conversion of methanol to olefins as well by co-feeding ketones. Olefinic products of the cyclization reaction are then oligomerized to a SAF blendstock to demonstrate an end-to-end ketone-to-SAF process facilitated by upgrading ketones over H/ZSM-5 at partial conversion with a recycle stream. The results of this work demonstrate a strategy to improve the carbon yield from bio-derived acids to SAF to over 75%, representing a relative improvement of more than 50% compared to previously reported data.

08 HYDROGEN

Redox Poise during Rhodospirillum rubrum Phototrophic Growth Drives Large-scale Changes in Macromolecular Synthesis Pathways

During photoheterotrophic growth on organic substrates, purple nonsulfur photosynthetic bacteria like Rhodospirillum rubrum can acquire electrons by multiple means, including oxidation of organic substrates, oxidation of inorganic electron donors (e.g., H2), and by reverse electron flow from the photosynthetic electron transport chain. These electrons are stored as reduced electron-carrying cofactors (e.g., NAD(P)H and ferredoxin). The overall ratio of oxidized to reduced cofactors (e.g., NAD(P)+:NAD(P)H), or ’redox poise’, is difficult to understand or predict, as are the cellular processes for dissipating these reducing equivalents. Using physics-based models that capture mass action kinetics consistent with the thermodynamics of reactions and pathways, a range of redox conditions for heterophototrophic growth are evaluated, from conditions in which the NADP+/NADPH levels approach thermodynamic equilibrium to conditions in which the NADP+/NADPH ratio is far above the typical physiological values. Modeling predictions together with experimental measurements indicate that the redox poise of the cell results in large-scale changes in the activity of biosynthetic pathways and, thus, changes in cell macromolecule levels (DNA, RNA, proteins, and fatty acids). Furthermore, modeling predictions indicate that during phototrophic growth, reverse electron flow from the quinone pool is a minor contributor to the production of reduced cofactors (e.g., NAD(P)H) compared to other oxidative processes (H2 and carbon substrate oxidation). Instead, the quinone pool primarily operates to aid ATP production. The high level of ATP, in turn, drives reduction processes even when NADPH levels are relatively low compared to NADP+ by coupling ATP hydrolysis to the reductive processes. The model, in agreement with experimental measurements of macromolecule ratios of cells growing on different carbon substrates, indicates that the dynamics of nucleotide versus lipid and protein production is likely a significant mechanism of balancing oxidation and reduction in the cell.

59 BASIC BIOLOGICAL SCIENCES

Redox poise in R. rubrum phototrophic growth drives large-scale changes in macromolecular pathways

During photoheterotrophic growth on organic substrates, purple nonsulfur photosynthetic bacteria like Rhodospirillum rubrum can acquire electrons by multiple means, including oxidation of organic substrates, oxidation of inorganic electron donors (e.g., H 2 ), and by reverse electron flow from the photosynthetic electron transport chain. These electrons are stored as reduced electron-carrying cofactors (e.g., NAD(P)H and ferredoxin). The overall ratio of oxidized to reduced cofactors (e.g., NAD(P)+:NAD(P)H), or ’redox poise’, is difficult to understand or predict, as are the cellular processes for dissipating these reducing equivalents. Using physics-based models that capture mass action kinetics consistent with the thermodynamics of reactions and pathways, a range of redox conditions for heterophototrophic growth are evaluated, from conditions in which the NADP+/NADPH levels approach thermodynamic equilibrium to conditions in which the NADP+/NADPH ratio is far above the typical physiological values. Modeling predictions together with experimental measurements indicate that the redox poise of the cell results in large-scale changes in the activity of biosynthetic pathways and, thus, changes in cell macromolecule levels (DNA, RNA, proteins, and fatty acids). Furthermore, modeling predictions indicate that during phototrophic growth, reverse electron flow from the quinone pool is a minor contributor to the production of reduced cofactors (e.g., NAD(P)H) compared to other oxidative processes (H 2 and carbon substrate oxidation). Instead, the quinone pool primarily operates to aid ATP production. The high level of ATP, in turn, drives reduction processes even when NADPH levels are relatively low compared to NADP+ by coupling ATP hydrolysis to the reductive processes. The model, in agreement with experimental measurements of macromolecule ratios of cells growing on different carbon substrates, indicates that the dynamics of nucleotide versus lipid and protein production is likely a significant mechanism of balancing oxidation and reduction in the cell.

59 BASIC BIOLOGICAL SCIENCES

Development of a Techno-Economic Analysis Framework for a Solar Thermochemical Fuel Production Process

Synthetic liquid fuels can provide a drop-in substitute for fossil-based fuels in sectors such as aviation and maritime, where electrification is not a viable option due to the need for high specific energy density. However, for these alternative fuels to be adopted at a commercial scale, their price must be competitive compared to their fossil-based counterparts. The reverse water-gas shift (RWGS) reaction offers a promising pathway, using hydrogen (sourced from electrolysis) and carbon dioxide as the feed and reacting to produce syngas - a mixture of H2 and CO at a specific ratio. Syngas is a useful precursor that can be converted into fuels and chemicals via known downstream processes, such as liquid transportation fuels via Fischer-Tropsch (FT) synthesis. The RWGS reaction is currently not applied in commercial scale, unlike the rest of the components in the process chain (electrolyzers and syngas-to-fuel synthesis units). The RWGS reaction poses several challenges due to its restrictive thermodynamics. Being an equimolar reaction, high temperatures and a large excess of H2 are needed to achieve reasonable CO2 conversion at equilibrium. This has detrimental effects on practical process implementation and the quality of syngas that can be produced, with direct effect on the energy and capital requirements, as well as the need for expensive downstream separation. In this work, we are proposing to develop a new concentrating solar thermal (CST) compatible RWGS reactor, performing the reaction in a 2-step chemical looping process using metal oxide at a temperature range of 600-800 degrees Celsius. By decoupling the reactor from the solar receiver, the Generation 3 (Gen3) CST technology could be utilized, together with its proposed thermal energy storage (TES) technology, benefitting from a good match to the required temperatures. CST technology is a viable option for supplying the heat that could be rapidly deployed in scale, thus being a good match to the gas-to-liquid (GTL) process which requires a large minimal scale to be commercially viable. The integration of TES with CST also allows operating the plant at large annual capacity factors and avoids multiple shutdown/startup cycles, thus fitting into the steady-state operation mode that most GTL processes require. The main innovation in the proposed design hinges on a countercurrent reaction design using a packed bed reactor. In 2019 Metcalfe et al. showed the benefits of countercurrent species exchange could be realized in a redox chemical-looping processes, by storing the favorable countercurrent chemical potential profiles in a packed bed of non-stoichiometric oxide. Metcalfe et al. applied this breakthrough concept to the WGS reaction, which is conventionally a co-feed catalytic process, showing a dramatic improvement. Bulfin et al. (2023) performed a similar proof-of-concept demonstration for the RWGS reaction using CeO2, achieving cumulative and peak CO2 conversions of 88% and 95%, respectively, compared to a thermodynamic limit of 58% for the co-feed catalytic process at the same conditions. In our new REGENLOOP project, we are developing a reactor prototype from the heat-exchange packed bed reactor-type, a commonly used reactor in the chemical industry. The endothermic heat of reduction will be supplied to the reactor using CST, while the same heat transfer fluid (HTF) mechanism will be used to extract the exothermic heat of oxidation. An array of multiple reactors is used to supply constant high-purity CO stream, that is then mixed with H2 from electrolysis to produce a high-purity syngas at the required composition. By removing the CO-CO2 separation after the RWGS process, significant energy and cost reduction can be achieved. A physics-based TEA framework is currently being developed, covering all the major plant processes, from the solar collection through storage, chemical looping RWGS, GTL, and auxiliary unit operations, up to the liquid hydrocarbon product. This modeling framework will utilize reduced-order models for the chemical looping RWGS and TES, CST modeling using SolarPILOT, and Aspen Plus for the GTL. By using this combined physics-based approach, the effects of design/operating parameters on the performance and cost can be elucidated. In our presentation, the modeling framework will be presented in detail, including preliminary cost predictions of using this plant configuration under a few selected relevant case studies. This study will be used to identify the major cost drivers, informing further system design and optimization needed to chart the way for a commercially viable pathway.

14 SOLAR ENERGY

Life Cycle Analysis of Natural Gas Supply Chain and End Use Applications in the United States

Natural gas (NG) plays a crucial role in current and future energy systems in the United States due to its abundance and affordability. In this study a life cycle analysis of the NG supply chain in the United States was conducted using Argonne's R&D GREET model, examining stages from recovery to distribution using reported field data processed and documented by National Energy Technology Laboratory. Supply chain emissions were evaluated across multiple spatial scales, including national average, overall regional production, region-to-region, and basin-to-region scenarios. The GHG intensity of the U.S. average NG supply chain was estimated at 10.3 kg CO 2 e/MMBtu (lower heating value), with a range across regions from 7.8 kg CO 2 e/MMBtu (Northeast) to 15.1 kg CO 2 e/MMBtu (Pacific). The analysis further assessed how upstream NG emissions influence the life cycle GHG emissions of key end-use applications, including electricity generation (0.044–0.086 kg CO 2 e/kWh from upstream NG in combined cycle facilities), hydrogen production (1.04–2.20 kg CO 2 e/kg H 2 for steam methane reforming [SMR] and 1.06–2.23 kg CO 2 e/kg for autothermal reforming [ATR]), and transit bus operation utilizing compressed natural gas fuel (0.19–0.37 kg CO 2 e/mile) and hydrogen fuel (0.12–0.25 kg CO 2 e/mile for hydrogen produced in SMR and ATR).

compression

AUTOIGNITION DELAY TIMES FOR REFORMATE GAS MIXTURES FROM METHANE GAS ENGINES

Methane slip is a prominent issue in natural gas reciprocating engines that are used in transportation and marine applications. The incomplete combustion that results in methane slip can be resolved with the introduction of hydrogen within the combustion mixture to improve methane oxidation and further enable combustion within the engine crevices where methane has previously remained unreacted. Steam methane reforming (SMR) is a common method used to produce hydrogen and can be used to design an onboard device to reduce methane slip from reciprocating engines. The development of this reformer device requires the validation of high-fidelity chemical kinetic models at the low temperatures of the crevice volumes of these engines. In this work, auto-ignition data is obtained using a shock tube at lean (φ—0.714 or λ—1.4) and stoichiometric (φ, λ = 1) equivalence ratios spanning a temperature range of 1042–1234 K at the 80-bar operating pressure of the test engine. Blends of methane, hydrogen, and reformate products from the SMR reaction are shock-heated in synthetic air, with the ignition delay time measured using an OH* chemiluminescence detector at 310 nm and a CH* detector at 430 nm. The experimental results are compared to several state-of-the-art chemical kinetic mechanisms from the literature. In general, most of the mechanisms show very good agreement with experiments at higher temperatures, with simulation results showing little deviation from experiments at lower temperatures. A sensitivity analysis was conducted, and the results reveal that the reaction H2 + CH3O2 = H + CH3O2H has a very significant role in determining low-temperature ignition delay times (IDTs) of SMR mixtures. These findings provide valuable insights into the chemical kinetics governing methane reformate combustion and contribute to the optimization of onboard reformer designs aimed at mitigating methane slip in natural gas-fueled engines.

Fraze, Matthew