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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Radiation-Induced Catalysis of Chemical Reactions

Nuclear energy is a process which achieves zero-carbon energy and heat generation that can provide a consistent electricity load to supply the grid when renewables are not available. However, on a cost per kilowatt-hour comparison, nuclear energy is more expensive than many of the renewable energy generation technologies such as wind and solar. In order to increase the economic viability of next generation nuclear reactors for energy production, generation of a secondary product such as a chemical feedstock would increase the economic viability of nuclear energy, particularly for new installations of next-generation nuclear reactors for power production. Currently, commercial nuclear reactors are primarily used for their heat to generate steam for electricity production. There is a large amount of unused energy in the form of photon and neutron radiation that could be exploited to drive chemical processes to produce feedstock materials as a secondary product of a nuclear plant. Chemical processing with radiation is not a new concept. In fact, gamma radiation is an excellent source of high energy photons to drive photochemical reactions. Dow chemical produced commercial quantities of ethyl bromide using gamma irradiation from a 60 Co source in the 1960s and 1970s because it was the most cost-effective means of production to meet the demand.5, 6 Due to the potential economic advantages, there is a new emphasis on studying feedstock production which can be enhanced by excess gamma and neutron radiation, particularly if the reaction could be monitored in real-time which is advantageous for process optimization. A model system of lignocellulose degradation under γ- radiation was chosen for this study while following the degradation products with Raman spectroscopy in real-time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Nanoscale Environments for Catalysis

The focus of this research program was to exploit new nanoscale environments in semiconductors as catalytic sites for programming reaction chemistry. Under the support of this program, the Nuckolls group created materials as catalysts with three interwoven major goals: (1) to explore new types of reactivity that is initiated and directed by electric fields in devices; (2) to explore photoredox in thin films of cellular semiconductors; (3) to develop a deep and fundamental understanding of the mechanism and mode of action of these new catalytic systems.

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

Aspatial Oxyanion Reduction Catalysis

The scientifically challenging problem of catalytically reducing oxyanions was explored and presented great opportunities in terms of the environment, economics and energy self-sufficiency. Oxyanions are pervasive as they are found in many areas of technology, all forms of life, in minerals, and as synthetic materials. Given their ubiquity, the contamination of inorganic oxyanions in drinking water is a national problem as 26 states and Puerto Rico have reported high concentrations of these harmful pollutants. The goals achieved by this research was to catalytically investigate the reduction of new oxyanions utilizing sustainable earth abundant catalysts featuring bio-inspired ligands. Further, ligand modifications will be explored to understand the impact on oxyanion reduction, mechanistic studies, and for electrocatalytic oxyanion reduction.

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

Integrating Chemical Catalysis and Biological Conversion of Carbon Intermediates for Deriving Value-Added Products from Carbon Dioxide

Carbon dioxide valorization represents an appealing approach to reducing greenhouse gases in the atmosphere. While electrocatalysis is an effective tool to reduce CO 2 into small carbon compounds, it becomes increasingly challenging to efficiently produce compounds with more carbon atoms. In contrast, while biological systems struggle to utilize CO 2 , they can readily upcycle other small carbon compounds. This project explores the use of a two-stage process that electrocatalytically converts CO 2 into methanol, formate, or acetate which is subsequently utilized by Methylotuvimicrobium alcaliphilum 20Z to produce medium chain length polyhydroxyalkanoate. A techno-economic analysis and life cycle assessment evaluates the commercial viability of the process as well as its carbon emissions. We show here an enhanced CO 2 -to-methanol electroconversion step coupled with the use of a microbial culture adapted to the process conditions to be the optimal configuration for economic potential.

09 BIOMASS FUELS↗
DOE OSTI2025

Propulsion of synthetic protocells and coacervates driven by biochemical catalysis

An important area in the design of biomolecular materials is the mimicry of cellular function through the assembly of molecular components into synthetic cells, or protocells. Through compartmentalization and subsequent evolution, biological cells have achieved the goals of specificity, amplification, and response. By assembling cell-like structures that mimic the organization and size of a natural cell but that incorporate novel components and respond to synthetic triggers, we can extend their capabilities beyond what is currently achievable in biology. For applications in energy, these include the ability to convert chemical to mechanical energy, and to enable the response of sensors and responders once a threshold has been reached. This technical report summarizes progress made on this project as of Dec 31, 2023.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Microwave Catalysis for Process Intensified Modular Production of Carbon Nanomaterials from Natural Gas

The objective of this project was to develop a novel, low-cost process intensified modular process to directly convert flare gas or stranded gas to carbon nanomaterials and co-product hydrogen (H 2 ) with high conversion, selectivity, and stability. The proposed project was based on our exciting exploratory research on a patent pending technology for one-step conversion of natural gas to carbon nanotubes (CNTs) and carbon fibers (CNFs) without emitting CO 2 : CH 4 → H 2 + C (CNT, Carbon Fibers).

03 NATURAL GAS↗
DOE OSTI2025

Multimodal Ligand Non-Innocence for Reduction Catalysis (Final Technical Report)

The goal of this project was to develop multimodal ligand non-innocence in late transition metal complexes of aminophenolate ligands and to apply this ligand-centered reactivity to small-molecule reduction reactions relevant to energy-conversion chemistry. Specific aims were, 1) Prepare new coordination complexes of aminophenolate ligands and characterize them using a battery of structural, spectroscopic, and computational methods. 2) Benchmark the thermodynamics and kinetics of e - , H + , H • , and H - transfer reactivity to establish the baseline reactivity of new metal complexes containing aminophenolate ligands. 3) Apply new aminophenolate complexes to catalytic reduction reactions.

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

The Role of Cooperative Interactions Among Surfaces, Solvents, and Reactive Intermediates on Catalysis at Liquid–Solid Interfaces (Final Report DE-SC0020224)

This project established quantitative links between inner‑sphere chemistry (active metal identity, coordination, and zeolite topology) and outer‑sphere organization (solvent identity, hydrogen‑bond networks, and pore condensation) that govern rates, activation barriers, and selectivities for alkene epoxidation and epoxide ring‑opening at solid–liquid and quasi‑liquid–solid interfaces. We deconvoluted contributions from covalent interactions at active sites and noncovalent, solvent‑mediated interactions within pores by pairing well‑defined metal substituted zeolites with controlled solvent environments. We then mapped those contributions onto measurable kinetics (ΔH‡, ΔS‡), adsorption thermodynamics (ITC), and in situ spectroscopy. The transferrable outcomes include a set of design rules that include the following understandings. First, tune silanol ((SiOH)x) density and pore topology to organize solvent networks that selectively stabilize transition states. Second, exploit activity‑coefficient‑normalized rates and adsorption– barrier correlations to diagnose when solvent reorganization rather than surface chemistry limits performance. Third, use partial pore condensation (e.g., acetonitrile, water but also generalizable to other solvents) to elicit liquid‑like stabilization effects even in nominally vapor‑phase reactors. Collectively, these results provide strategies to increase epoxidation rates, improve oxidant utilization (i.e., selectivities), and steer regioselectivity in zeolite‑based catalytic processes relevant to sustainable oxidation chemistry. These outcomes should be transferable to other classes of reactions that proceed in microporous materials and under confinement provided by organized solvents (e.g., electrochemical double layers).

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

The moderately defficient enzyme: Catalysis-related damage in vivo and its repair

Enzymes have in vivo lifespans. Analysis of lifespans – lifetime totals of catalytic turnovers – suggests that non-survivable collateral chemical damage from the very reactions that enzymes catalyze is a common but underdiagnosed cause of enzyme death. Analysis also implies that many enzymes are moderately deficient in that their active-site regions are not naturally as hardened against such collateral damage as they could be, leaving room for improvement by rational design or directed evolution. Enzyme lifespan might also be improved by engineering systems that repair otherwise fatal active-site damage, of which a handful are known and more are inferred to exist. Unfortunately, the data needed to design and execute such improvements is lacking: there are too few measurements of in vivo lifespan, and existing information on the extent, nature, and mechanisms of active-site damage and repair during normal enzyme operation is too scarce, anecdotal, and speculative to act on. Fortunately, advances in proteomics, metabolomics, cheminformatics, comparative genomics, and structural biochemistry now empower a systematic, data-driven approach to identify, predict, and validate instances of active-site damage and its repair. These capabilities would be practically useful in enzyme redesign and improvement of in-use stability, and could change thinking about which enzymes die young in vivo, and why.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

The moderately defficient enzyme: Catalysis-related damage in vivo and its repair

Enzymes have in vivo lifespans. Analysis of lifespans – lifetime totals of catalytic turnovers – suggests that non-survivable collateral chemical damage from the very reactions that enzymes catalyze is a common but underdiagnosed cause of enzyme death. Analysis also implies that many enzymes are moderately deficient in that their active-site regions are not naturally as hardened against such collateral damage as they could be, leaving room for improvement by rational design or directed evolution. Enzyme lifespan might also be improved by engineering systems that repair otherwise fatal active-site damage, of which a handful are known and more are inferred to exist. Unfortunately, the data needed to design and execute such improvements is lacking: there are too few measurements of in vivo lifespan, and existing information on the extent, nature, and mechanisms of active-site damage and repair during normal enzyme operation is too scarce, anecdotal, and speculative to act on. Fortunately, advances in proteomics, metabolomics, cheminformatics, comparative genomics, and structural biochemistry now empower a systematic, data-driven approach to identify, predict, and validate instances of active-site damage and its repair. These capabilities would be practically useful in enzyme redesign and improvement of in-use stability, and could change thinking about which enzymes die young in vivo, and why.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Bifunctional Heterometallic Metal-Organic Frameworks for Solvent-Free Heterogeneous Cascade Catalysis

A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

SABRE Ir-IMes Catalysis for the Masses

The Signal Amplification By Reversible Exchange (SABRE) technique provides enhancement of Nuclear Magnetic Resonance (NMR) signals up to several orders of magnitude using chemical exchange of a substrate and parahydrogen on an iridium complex. Therefore, the availability of such a catalytic complex to a broader community is an absolutely vital step for dissemination of the groundbreaking SABRE methodology. The most common SABRE catalyst, which is activated in situ, is based on Ir-IMes system (IMes = 1,3-Bis(2,4,6-trimethylphenyl)imidazol-2-ylidene). Earlier approaches for the synthesis of this catalyst often relied on specialized equipment and were limited to a comparatively small scale. This, in turn, increased the barrier of entry for new scientists to the area of SABRE hyperpolarization. Here, we present a robust, inexpensive, and easy to reproduce synthetic procedure for the preparation of this SABRE catalyst, which does not require specialized inert atmosphere equipment like a glove box or Schlenk line. The synthesis was validated on the scale of several grams vs. tens of milligrams scale in the reported approaches. The resulting SABRE catalyst, [Ir(IMes)(COD)Cl], was activated in situ and further evaluated in hyperpolarization experiments resulting in signal enhancements comparable to (or higher than) those for the catalyst prepared using Schlenk line equipment.

Biochemistry & Molecular Biology↗
DOE OSTI2020

Atomic Layer Deposition for Preparing Isolated Co Sites on SiO 2 for Ethane Dehydrogenation Catalysis

Unlike Co clusters, isolated Co atoms have been shown to be selective for catalytic dehydrogenation of ethane to ethylene; however, preparation of isolated Co sites requires special preparation procedures. Here, we demonstrate that Atomic Layer Deposition (ALD) of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(III) (Co(TMHD) 3 ) on silica and other supports is effective in producing these isolated species. Silica-supported catalysts prepared with one ALD cycle showed ethylene selectivities greater than 96% at 923 K and were stable when CO 2 was co-fed with the ethane. Co catalysts prepared by impregnation formed clusters that were significantly less active, selective, and stable. Rates and selectivities also decreased for catalysts with multiple ALD cycles. Isolated Co catalysts prepared on Al 2 O 3 and MgAl 2 O 4 showed reasonable selectivity for ethane dehydrogenation but were not as effective as their silica counterpart.

36 MATERIALS SCIENCE↗