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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

The inorganic chemist's guide to actinide radiation chemistry: a review

This review aims to provide an overview of the current state of radiation chemistry with respect to the actinide elements, thorium through californium. Despite the inherent radioactivity of the actinides, only a few studies explore the effects of ionizing radiation on their redox chemistry and surrounding environment. This fundamental knowledge gap, coupled with the current renaissance in actinide-based technologies such as nuclear power, space exploration, and medicine, underscores the importance of research in this interdisciplinary area. This review will focus on the interactions between reactive species formed by radiolysis with actinides and their complexes, offering an inorganic chemist's perspective on research in radiation chemistry. In addition, a thorough discussion of our current understanding of radiation-induced changes in actinide speciation in both aqueous solution and the solid-state will be provided, focusing on changes in oxidation state distribution, complexation, and secondary coordination effects within inorganic materials. Finally, this review will discuss challenges and opportunities for inorganic chemists to explore this unique intersection of fields.

Actinides↗
DOE OSTI2020

Anomalous Anisotropic Nanoparticle Aggregation in Cu 2 (OH) 3 Br Gels

Aerogels are of interest for their ability to uniformly incorporate nanoscale features into macroscopic assemblies, which enabled applications that require low density, high surface area, and/or bicontinuous networks. The structure of the nanoporous network is intrinsically linked to the macroscopic properties of aerogels. Hence, control of this structure is of paramount importance. Small-angle X-ray scattering (SAXS) is used here to monitor nanoparticle aggregation in situ in Cu 2 (OH) 3 Br aerogels formed via epoxide-assisted gelation. Anomalous anisotropic aggregation is observed in the absence of templating agents and is attributed to the molecular structure of the inorganic nanoparticles themselves. This is a fundamental departure from the models currently used to describe traditional inorganic sol–gel chemistry where nanoparticles are believed to undergo isotropic diffusion- and/or kinetically limited aggregation. Time-resolved SAXS indicates that Cu 2 (OH) 3 Br nanoparticles nucleate rapidly from solution to form unbranched chain-like aggregates rather than branched mass-fractal aggregates. Sizes of primary particles (~1.5 nm) and the chain-like structure of their aggregates are independent of particle concentration (gel density), while rates of particle aggregation, gelation time, and aggregate size are strongly dependent upon particle concentration, which implies that the chemistry of particle formation and the physics of particle aggregation are independent processes. Because the conditions necessary for creating anisotropic structures are not unique to Cu 2 (OH) 3 Br, these results could provide insight into the structure and gelation mechanisms of other inorganic aerogels.

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

The effect of varying powder feedstock chemistry and printing atmosphere on the microstructure of additively manufactured nickel-based ODS alloys: Role on stabilization of cellular structures vs. oxide dispersion formation

Nickel-based alloys have a wide variety of structural applications due to their high corrosion resistance and mechanical strength which depend on solid solution strengthening, or the formation of oxides and/or intermetallic precipitation for their properties. In this study, the microstructure of six Ni–Cr–Y–Ti–Al powder batches designed for the production of oxide dispersion strengthened nickel were compared. These batches varied in chemistry and atomization technique used which included Gas Atomization Reactive Synthesis (GARS). The batches of powder were then consolidated via Additive Manufacturing (AM) Powder Bed Fusion using Laser Beam (PBF-LB) and characterized via transmission electron microscopy to elucidate the influence of powder feedstock (i.e. synthesis methodology and chemistry) on the PBF-LB microstructure. The study investigates (i) how the amount of yttrium and titanium additions in the powder feedstock and the addition of oxygen during the processing (through GARS) affect the microstructure of the powder itself and the AM printed microstructure, and (ii) how the control of oxygen addition in the printing atmosphere during the PBF-LB printing process itself is another important parameter for achieving the formation of the wanted oxide dispersion versus the stabilization of the cellular structure (often observed in AM processed alloys). Microstructural characterization of both powder particles and additively manufactured nickel alloys in this study provide important insights into the movement of yttrium within the material upon solidification, particularly along cell boundaries, and how yttrium behaves depending on alloy chemistry. When a threshold of yttrium content is reached within the system, yttrium consistently reacts to form an intermetallic along cell boundaries instead of forming oxide nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Zero and Finite Temperature Quantum Simulations Powered by Quantum Magic

We introduce a quantum information theory-inspired method to improve the characterization of many-body Hamiltonians on near-term quantum devices. We design a new class of similarity transformations that, when applied as a preprocessing step, can substantially simplify a Hamiltonian for subsequent analysis on quantum hardware. By design, these transformations can be identified and applied efficiently using purely classical resources. In practice, these transformations allow us to shorten requisite physical circuit-depths, overcoming constraints imposed by imperfect near-term hardware. Importantly, the quality of our transformations is t u n a b l e : we define a 'ladder' of transformations that yields increasingly simple Hamiltonians at the cost of more classical computation. Using quantum chemistry as a benchmark application, we demonstrate that our protocol leads to significant performance improvements for zero and finite temperature free energy calculations on both digital and analog quantum hardware. Specifically, our energy estimates not only outperform traditional Hartree-Fock solutions, but this performance gap also consistently widens as we tune up the quality of our transformations. In short, our quantum information-based approach opens promising new pathways to realizing useful and feasible quantum chemistry algorithms on near-term hardware.

Physics↗
DOE OSTI2025

TALSPEAK-based separation of the trivalent actinides from rare earth elements using LN resin

The separation of 241 Am, 244 Cm and 249 Cf from rare earth elements using LN resin and lactate buffer solutions with diethylenetriaminepentaacetic acid is described with numerous columns studies. The elutions are based on TALSPEAK liquid–liquid extraction chemistry, and provide high yield (> 90%), rapid, simple separations of the trivalent actinides from the lanthanides, which is often challenging due to similarities in chemical behavior among the trivalent f-block elements. Further, all three actinides can be separated from rare earth elements, including from massless fission product samples and samples with small amounts (~ 1–5 mg) of stable lanthanides. Separations with no detectable overlap between the actinide and lanthanide elutions is possible with massless samples, and in samples with mass high separation factors can be achieved (Am/Eu: 171; Am/La: 10 6 ).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Phase Transformation Mechanism of Amorphous Calcium Phosphate to Hydroxyapatite Investigated by Liquid-Cell Transmission Electron Microscopy

Crystallization via phase transformation of a metastable precursor is a ubiquitous and effective strategy used by living systems to direct the growth of crystalline nanomaterials with remarkable functional properties. However, determining the exact process by which transformation occurs at the nanoscale is a difficult challenge. In this work, the recrystallization process of amorphous calcium phosphate (ACP) to hydroxyapatite (HAP) is explored by liquid-cell transmission electron microscopy. The effect of confinement in the liquid-cell is found to increase the size of ACP nanoparticles. In the presence of Mg 2+ , these large ACP nanoparticles transform to HAP by first dissolving from the interior to create a hollow structure, after which HAP forms preferentially on the surface and then subsequently in the bulk solution. We propose that the preferential dissolution within ACP particles is due to a change in the structure and/or chemistry of the ACP surface, likely associated with dehydration before crystallization of HAP. These results imply an important role of the confined environment of the liquid-cell in regulating the size of ACP particles, which then affects the surface structure and the detailed dissolution–recrystallization pathway. Moreover, we stress the key role of Mg 2+ in controlling HAP formation by stabilizing ACP via reduction in ACP solubility. This work provides a better understanding of the roles of additives and confinement during the phase transformation of ACP to HAP through dissolution and recrystallization.

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

Inexpensive Hydrogen Storage: Propylene to Propane using Plasmonic Photocatalysis

Chemistry-based hydrogen storage media, such as liquid organic hydrogen carriers, offer an attractive alternative to physical hydrogen storage solutions. Here, we investigate propane as a possible hydrogen storage medium, attractive for its low cost and ease of availability. We report the ambient temperature and pressure hydrogenation of propylene using an antenna-reactor Al@TiO 2 −Pt single-atom plasmonic photocatalyst. Illumination at two distinct wavelengths, 450 and 800 nm, corresponds to high reactivity toward propane production. Theoretical insight into wavelength-dependent hot-carrier generation reveals nonequilibrium carriers with sufficient energies to activate both steps of propylene hydrogenation at either wavelength, the dissociation of H 2 and its incorporation into the propylene carbon− carbon double bond. Paired with light-driven propane dehydrogenation, this study demonstrates that photocatalytic cycling of propylene - propane for hydrogen storage and release can be performed under mild conditions.

alkyls↗
DOE OSTI2025

Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte

Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO 4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO 4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO 4 to NaFePO 4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (~2.4 V) at the end of the discharge process of the FePO 4 ||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF 6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO 4 to form single-phase Na 0.9 FePO 4 . Na 0.9 FePO 4 ||hard carbon full cells demonstrated a remarkable capacity retention of ~84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spitfire

Spitfire is a Python and C++ code for solving canonical flame structure problems to build tabulated chemistry models for the simulation of large-scale fires. Spitfire is a modular software with performance critical code written in C++, abstract numerical methods provided in Python, and chemistry tabulation techniques made convenient for high-level use by non-expert users. It facilitates both high-level usage and novel research in tabulated chemistry approaches. SAND2019-11791 M Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Armstrong, Elizabeth↗
DOE OSTI2023

Control of Cement Timing, Mineralogy, and Texture on Hydro-chemo-mechanical Coupling from CO2 Injection into Sandstone: A Synthesis

Carbon capture, utilization, and storage (CCUS) has been widely applied to enhance oil recovery (CO2-EOR). A thorough investigation of the impact of injecting CO2 into a heterogeneous reservoir is critical to understanding the overall reservoir robustness and storage performance. We conducted fifteen flow-through tests on Morrow B sandstone that allowed for chemical reactions between a CO2-rich brackish solution and the sandstones, and four creep/flow-through tests that simultaneously allowed for chemical reactions and stress monitoring. From fluid chemistry and X-ray computed tomography, we found that the dissolution of disseminated cements and the precipitation of iron-rich clays did not significantly affect the permeability and geomechanical properties. Minor changes in mechanical properties from Brazilian and creep tests indicated that the matrix structure was well-supported by early diagenetic quartz overgrowth cement and the reservoir’s compaction history at deep burial depths. However, one sample experienced a dissolution of poikilotopic calcite, leading to a permeability increase and significant tensile strength degradation due to pore opening, which overcame the effect of the early diagenetic cements. We concluded that the Morrow B sandstone reservoir is robust for CO2 injection. Most importantly, cement timing, the abundance and texture of reactive minerals, and the reservoir’s burial history are critical in predicting reservoir robustness and storage capacity for CO2 injection.

Wu, Zhidi (ORCID:0000000338869492)↗
DOE OSTI2022

Aqueous titanium redox flow batteries—State-of-the-art and future potential

Market-driven deployment of inexpensive (but intermittent) renewable energy sources, such as wind and solar, in the electric power grid necessitates grid-stabilization through energy storage systems Redox flow batteries (RFBs), with their rated power and energy decoupled (resulting in a sub-linear scaling of cost), are an inexpensive solution for the efficient electrochemical storage of large amounts of electrical energy. Titanium-based RFBs, first developed by NASA in the 1970s, are an interesting albeit less examined chemistry and are the focus of the present review. Ti, constituting 0.6% of the Earth’s crust and an ingredient in inexpensive white paints, is amongst the few elements (V and Mn being some others) which exhibit multiple soluble oxidation states in aqueous electrolytes. Further, the very high (approaching 10 M) solubility of Ti in low pH solutions suggests the possibility of developing exceptionally high energy density aqueous Redox Flow Batteries systems. With these advantages in mind, we present the state-of the-art in Ti-RFBs with a focus on Ti/Mn, Ti/Fe and Ti/Ce couples and systems that use Ti as an additive (such as Ti/V/Mn). The inherent advantages of inexpensive Ti actives and relatively high energy density is contrasted with potential side-reactions resulting in reduced energy efficiency. Technological pathways are presented with a view to overcoming critical bottlenecks and a vision is presented for the future development of Ti-RFBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Can electric fields drive chemistry for an aqueous microdroplet?

Abstract Reaction rates of common organic reactions have been reported to increase by one to six orders of magnitude in aqueous microdroplets compared to bulk solution, but the reasons for the rate acceleration are poorly understood. Using a coarse-grained electron model that describes structural organization and electron densities for water droplets without the expense of ab initio methods, we investigate the electric field distributions at the air-water interface to understand the origin of surface reactivity. We find that electric field alignments along free O–H bonds at the surface are ~16 MV/cm larger on average than that found for O–H bonds in the interior of the water droplet. Furthermore, electric field distributions can be an order of magnitude larger than the average due to non-linear coupling of intramolecular solvent polarization with intermolecular solvent modes which may contribute to even greater surface reactivity for weakening or breaking chemical bonds at the droplet surface.

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

Aqueous Interfaces in Chemical Separations

Chemical separations play a vital role in refinery and reprocessing of critical materials, such as platinum group metals, rare earths, and actinides. The choice of separation system─whether it is liquid–liquid extraction (LLE), sorbents, or membranes─depends on specific needs and applications. In almost all separation processes, the desired metal ions adsorb or transfer across an aqueous interface, such as the solid/liquid interface in sorbents or oil/water interfaces in LLE. Despite these separation technologies being extensively used for decades, our understanding of the molecular-scale mechanisms governing ion adsorption and transport at interfaces remains limited. This knowledge gap presents a significant challenge in meeting the increasing demands for these critical materials due to their growing use in advanced technologies. Fortunately, recent advancements in surface-specific experimental and computational techniques offer promising avenues to bridge this gap and facilitate the development of next-generation separation systems. Interestingly, unanswered questions regarding interfacial phenomena in chemical separations hold great relevance to various fields, including energy storage, geochemistry, and atmospheric chemistry. Therefore, the model interfacial systems developed for studying chemical separations, such as amphiphilic molecules assembled at a solid/water, air/water, or oil/water interface, may have far-reaching implications, extending beyond separations and opening doors to addressing a wide range of scientific inquiries. This perspective discusses recent interfacial studies elucidating amphiphile–ion interactions in chemical separations of metal ions. Finally, these studies provide direct, molecular-scale information about solute and solvent behavior at aqueous interfaces, including multivalent and complex ions in highly concentrated solutions, which play key roles in LLE of critical materials.

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

Dynamics of Aqueous Electrolyte Solutions: Challenges for Simulations

This Perspective article focuses on recent simulation work on the dynamics of aqueous electrolytes. It is well-established that full-charge, nonpolarizable models for water and ions generally predict solution dynamics that are too slow in comparison to experiments. Models with reduced (scaled) charges do better for solution diffusivities and viscosities but encounter issues describing other dynamic phenomena such as nucleation rates of crystals from solution. Polarizable models show promise, especially when appropriately parametrized, but may still miss important physical effects such as charge transfer. First-principles calculations are starting to emerge for these properties that are in principle able to capture polarization, charge transfer, and chemical transformations in solution. Finally, while direct ab initio simulations are still too slow for simulations of large systems over long time scales, machine-learning models trained on appropriate first-principles data show significant promise for accurate and transferable modeling of electrolyte solution dynamics.

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

Local electronic structure of histidine in aqueous solution

Here, the local electronic structure of aqueous histidine, an amino acid important in nature and biology, is revealed by aerosol X-ray photoemission spectroscopy. A detailed picture of the photoionization dynamics emerges by tuning the pH of the aqueous solution from which the aerosols are generated, allowing us to report the X-ray photoelectron spectroscopy (XPS) of histidine. Assignment of the experimental photoelectron spectra of the C1s and N1s levels allows the determination of the protonation state of histidine in these aqueous aerosols and is confirmed by density functional calculations. XPS spectra show that at pH = 1, both imidazole and amine group nitrogens are protonated, at pH = 7, the amine group nitrogen is protonated and the carboxyl group carbon is deprotonated resulting in a zwitterionic structure, and at pH = 13, only the carboxyl group remains deprotonated. Comparison of these results with previous experimental and theoretical results suggests that X-ray spectroscopy on aqueous aerosols can provide a convenient and simple way of probing their electronic structure in aqueous solutions.

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

Achieving industrial ammonia synthesis rates at near-ambient conditions through modified scaling relations on a confined dual site

The production of ammonia through the Haber–Bosch process is regarded as one of the most important inventions of the 20th century. Despite significant efforts in optimizing the process, it still consumes 1 to 2% of the worldwide annual energy for the high working temperatures and pressures. The design of a catalyst with a high activity at milder conditions represents another challenge for this reaction. Herein, we combine density functional theory and microkinetic modeling to illustrate a strategy to facilitate low-temperature and -pressure ammonia synthesis through modified energy-scaling relationships using a confined dual site. Our results suggest that an ammonia synthesis rate two to three orders of magnitude higher than the commercial Ru catalyst can be achieved under the same reaction conditions with the introduction of confinement. Such strategies will open pathways for the development of catalysts for the Haber–Bosch process that can operate at milder conditions and present more economically viable alternatives to current industrial solutions.

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

SPRUCE Precipitation Chemistry and Bulk Atmospheric Deposition Beginning in 2013

This data set reports the chemistry of precipitation water that was collected at the SPRUCE site located in the S1 bog and calculated values of bulk atmospheric deposition of solutes in precipitation. Sample collection and analyses started during December of 2013 and will continue for the duration of the experiment. Precipitation samples were collected year round on an event-basis from up to three individual collectors. Samples were either composited or individually analyzed, depending on the total volume of water available relative to the amount needed to complete all laboratory analyses. Funnel/bottle collectors were used to collect rainfall and buckets were used to collect snowfall and mixed precipitation. Samples were analyzed for pH, specific conductivity, nutrient concentrations (ammonium, nitrate, soluble reactive phosphorus, total nitrogen), cation concentrations (calcium, magnesium), anion concentrations (chloride, sulfate), total organic carbon concentrations, and natural-abundance stable isotopes of water (δ18O-H2O and δD-H2O). Bulk deposition was calculated by multiplying rainfall amount by solute concentration for ammonium, nitrate, soluble reactive phosphorus (SRP), total nitrogen, calcium, magnesium, chloride, sulfate, and total organic carbon. All measurements were made at the 8.1-ha S1 bog forest site in northern Minnesota, 40 km north of Grand Rapids, in the USDA Forest Service Marcell Experimental Forest (MEF).

54 ENVIRONMENTAL SCIENCES↗