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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The Role of Alkalis in Orchestrating Uranyl-Peroxide Reactivity Leading to Direct Air Capture of Carbon Dioxide

Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, in this work, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb + and Cs + salts (Cs-U 1 and Rb-U 1 ). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li + , Na + and K + analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U 1 , the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO 2 in the solid-state, converting to Cs 4 [U VI O 2 (CO 3 ) 3 ], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U 1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsU V O 3 , where the parent phase has been computationally predicted, but not yet synthesized.

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

Modelling and analysis of salt-convection effect on oxide reduction process for uranium oxides using smoothed particle hydrodynamics

Oxygen ion transport via molten salt continuum is a key kinetic feature of electrochemical reduction process for uranium oxides in molten salt. During the electrolysis, the evolution of oxygen ion concentration field in molten salt continuum appears from porous metallic layer to open bulk salt. Despite the important role affecting process throughput, its effect coupled with controlled salt movement was not adequately investigated. To capture the reactive oxygen ion transport phenomena, a multidimensional reduction model based on smoothed particle hydrodynamics (SPH) was combined with the advection-diffusion model. A pelletized oxide fuel bed capturing interconnected salt continuum is considered as a reactant material geometry, which allows forced convective delivery of molten salt through the reactant materials with a relatively low pressure head. Here, in this study, reduction time of a pelletized-fuel bed was quantified with respect to key design parameters of the reactant material configuration. The simulation results demonstrated the advantage of salt convection which effectively removes oxygen ion products from the reactant materials and consequently accelerates the reduction process. Moreover, the reduction-time correlation of a single pelletized fuel was developed as a function of relevant dimensionless parameters and was extended to the application for a pelletized-fuel bed. Finally, several insights and implications in the use of a pelletized oxide fuel were presented. The developed SPH-based framework enabled multi-physics analysis of governing dynamics in appreciating and screening candidate reactant material configurations in a cost-effective manner.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Implementing vanadium peroxides as direct air carbon capture materials

Vanadium peroxide molecules undergo stoichiometric direct air capture of carbon dioxide, wherein reactivity towards carbon capture via both peroxide and adventitious superoxide ligands trends with the size of the alkali countercation.

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

Efficient Synthetic Natural Gas Production from Direct Air Capture Using Titania-Based Dual Function Materials

Converting atmospheric CO2 into methane offers a compelling pathway to store intermittent renewable electricity and enhance energy security using existing natural gas infrastructure. However, current CO2 utilization approaches remain energy- and capital-intensive, largely due to the need for separate capture, purification, and conversion steps. Integrating CO2 capture with catalytic methanation represents a transformative strategy for process intensification on both the unit operation and molecular levels. We report a series of Ru-Na/TiO2 dual function materials (DFMs) for a reactive carbon capture (RCC) process consisting of simulated direct air capture and subsequent CO2 methanation (DACM). Superior methane desorption purity was observed on TiO2-based DFMs (>94 %) relative to state-of-the-art Al2O3-supported DFMs (77 %). Modifying the process to begin CO2 adsorption immediately following the methanation stage, rather than beginning adsorption near ambient temperature, resulted in >97 % methane desorption purity, suitable for injection into the natural gas pipeline without additional CO2 separation steps.

organic↗
DOE OSTI2025

Photoreactive Capture and Conversion of Dilute Carbon Dioxide into Synthetic Natural Gas

This study introduces a photoreactive system that integrates the capture of dilute CO 2 streams with their catalytic conversion to synthetic natural gas (CH 4 ), utilizing a Ru nanoparticle (NP)-doped TiO 2 composite loaded with linear polyethylenimine (L-PEI) and enhanced with plasmonic titanium nitride (TiN). This light-driven approach mitigates challenges that have plagued traditional thermal reactive carbon capture (RCC) methods, such as CO 2 slip and amine degradation. We demonstrate that L-PEI enables stable CO 2 capture and conversion, achieving ~70% conversion of captured CO 2 to CH 4 across multiple reaction cycles using nonflammable forming gas (~5% H 2 ) as the reductant. In contrast, branched PEI (B-PEI)-loaded composites exhibited significant catalyst deactivation after several RCC cycles. Scanning transmission electron microscopy (STEM) imaging confirms that significant sintering of the Ru NPs occur in the B-PEI sample under RCC conditions, whereas their size remains stable in more rigid L-PEI composites. Technoeconomic analysis (TEA) estimates that CH 4 production using this system could cost less than $\$$5/kg based on current electrocatalytic H 2 prices. These results represent one of the most promising demonstrations of amine-based RCC employing dilute CO 2 sources to date.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Deep Learning Modeling Framework to Capture Mixing Patterns in Reactive-Transport Systems

Prediction and control of chemical mixing are vital for many scientific areas such as subsurface reactive transport, climate modeling, combustion, epidemiology, and pharmacology. Due to the complex nature of mixing in heterogeneous and anisotropic media, the mathematical models related to this phenomenon are not analytically tractable. Numerical simulations often provide a viable route to predict chemical mixing accurately. However, contemporary modeling approaches for mixing cannot utilize available spatial-temporal data to improve the accuracy of the future prediction and can be compute-intensive, especially when the spatial domain is large and for long-term temporal predictions. To address this knowledge gap, in this work we will present in this paper a deep learning (DL) modeling framework applied to predict the progress of chemical mixing under fast bimolecular reactions. This framework uses convolutional neural networks (CNN) for capturing spatial patterns and long short-term memory (LSTM) networks for forecasting temporal variations in mixing. By careful design of the framework—placement of non-negative constraint on the weights of the CNN and the selection of activation function, the framework ensures non-negativity of the chemical species at all spatial points and for all times. Our DL-based framework is fast, accurate, and requires minimal data for training. The time needed to obtain a forecast using the model is a fraction (≈ O(-6)) of the time needed to obtain the result using a high-fidelity simulation. To achieve an error of 10% (measured using the infinity norm) for capturing local-scale mixing features such as interfacial mixing, only 24% to 32% of the sequence data for model training is required. To achieve the same level of accuracy for capturing global-scale mixing features, the sequence data required for model training is 64% to 70% of the total spatial-temporal data. Hence, the proposed approach—a fast and accurate way to forecast long-time spatial-temporal mixing patterns in heterogeneous and anisotropic media—will be a valuable tool for modeling reactive-transport in a wide range of applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Mutation of active site glutamate in serine hydroxymethyltransferase allows trapping a reactive intermediate: a combined neutron and X-ray crystallography study

Serine hydroxymethyltransferase (SHMT) is a pyridoxal-5′-phosphate (PLP) dependent enzyme that catalyzes a chemical transformation essential for the one-carbon (1C) metabolism. SHMT reversibly converts L-Ser into Gly and transfers a 1C unit to tetrahydrofolate (THF) to give 5,10-methylene-THF (5,10-MTHF). 5,10-MTHF, a 1C-unit donor, plays a crucial role in the downstream biomolecular syntheses required for the cell homeostasis and proliferation. SHMT is a prominent target for the drug discovery to battle bacterial and parasitic infections, and to treat various types of cancer. SHMT-catalyzed chemistry is governed by the general acid-base catalysis. Knowledge of the catalytic mechanism can aid drug design but can only be achieved when the atomic details of each reaction step are mapped, including accurate determination of hydrogen atom positions. Here we utilized the inactive E53Q mutant of Thermus thermophilus ( Tth ) SHMT to directly determine protonation states with room-temperature neutron crystallography and to capture a reactive intermediate containing the PLP-L-Ser external aldimine and THF in the enzyme active site. We observed protonation of the Schiff base nitrogen (N SB ) in the PLP internal aldimine but no change in the protonation states of other ionizable PLP groups and active site residues compared to wild-type Tth SHMT. X-ray structural analysis of the ternary intermediate complex E53Q-Ser-THF that eluded previous structural characterization shows the strategic positioning of the E53Q side chain in close proximity to the external aldimine and THF and reinforces the proposed role for E53 as the driver of proton transfer events along the reaction pathway.

Drago, Victoria N. [Oak Ridge National Laboratory ↗
DOE OSTI2022

Assessing the role of surface carbon on the surface stability and reactivity of β-Mo 2 C catalysts

Transition-metal carbides, e.g., Mo 2 C, promote industrially important catalytic reactions with activities comparable to precious-metal catalysts. Yet, the nature of the catalytically active sites remains unclear. Herein, density functional theory calculations are applied to systematically assess the stability of low-Miller index facets of β-Mo 2 C as a function of carbon chemical potential (uC) and surface-carbon coverage (nC). When reconstruction of surface carbon is considered to characterize β-Mo 2 C under varying environments, the (111) and (101) surfaces are predicted to be most stable, dominating the Wulff particle surface area across a broad range of uC. The surface-carbon coverage is predicted to steadily increase for all low-index facets under more carburizing reaction conditions, leading to distinct effects on the adsorption energetics for atomic hydrogen and oxygen. Whereas H binding is only slightly affected by surface carbon, O is systematically destabilized. The findings reported indicate that consideration of only bulk-terminated surfaces, and the common focus of theoretical studies on the bulk-truncated, close-packed (100) surface, is likely insufficient to capture the reactivity of the working ..beta..-Mo 2 C catalyst. Similar to metal oxides, β-Mo2C catalysts are predicted to be dynamic materials with surface compositions and reactivities that evolve in response to the environment.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electrocatalysis in CO 2 -Binding Organic Liquids with an Iron Porphyrin

Direct electrochemical upgrading of CO 2 in capture media is an attractive approach to carbon capture that can bypass the energy requirement for the thermal release of pure CO 2 . Here we investigate the electrocatalytic activity of iron(tetraphenylporphyrin) in the presence of organic solvents that convert into ionic liquids upon exposure to CO 2 . Four different solvent systems were tested, all of which capture CO 2 in the form of an alkyl carbonate (or carbamate) anion and an acidic ammonium cation. The electrocatalytic selectivity exhibited a strong dependence on the acidity of the capture medium, with the most basic solvent affording a high selectivity for production of CO instead of H 2 . Experimental and computational studies support a canonical mechanism in which the catalyst reacts with free CO 2 in solution, as opposed to a reaction with the alkyl carbonate that is present in high concentration. Kinetic analysis indicates that the rate-limiting step is changed from C–O protonolysis in traditional solvents to the binding of CO 2 in the capture media. Quantitative 13 C– 13 C EXSY revealed that the dissociation of the alkyl carbonate into free, solvated CO 2 is very rapid (~15 s –1 ) compared to the interconversion of HCO 3 – /CO 2 in aqueous solution. These results underscore the need to understand the mechanism and kinetics for both the release of captured CO 2 and its electrocatalytic conversion.

Carbon Dioxide↗
DOE OSTI2020

Computationally Directed Discovery of MoBi 2

Incorporating bismuth, the heaviest element stable to radioactive decay, into new materials enables the creation of emergent properties such as permanent magnetism, superconductivity, and nontrivial topology. Understanding the factors that drive Bi reactivity is critical for the realization of these properties. Using pressure as a tunable synthetic vector, we can access unexplored regions of phase space to foster reactivity between elements that do not react under ambient conditions. Furthermore, combining computational and experimental methods for materials discovery at high-pressures provides broader insight into the thermodynamic landscape than can be achieved through experiment alone, informing our understanding of the dominant chemical factors governing structure formation. Herein, we report our combined computational and experimental exploration of the Mo–Bi system, for which no binary intermetallic structures were previously known. Using the ab initio random structure searching (AIRSS) approach, we identified multiple synthetic targets between 0–50 GPa. Highpressure in situ powder X-ray diffraction experiments performed in diamond anvil cells confirmed that Mo–Bi mixtures exhibit rich chemistry upon the application of pressure, including experimental realization of the computationally predicted CuAl 2 -type MoBi 2 structure at 35.8(5) GPa. Electronic structure and phonon dispersion calculations on MoBi 2 revealed a correlation between valence electron count and bonding in high-pressure transition metal–Bi structures as well as identified two dynamically stable ambient pressure polymorphs. Our study demonstrates the power of the combined computational–experimental approach in capturing highpressure reactivity for efficient materials discovery.

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

Moisture-driven CO 2 direct air capture and delivery for cultivating cyanobacteria

This study demonstrates a low-energy system that passively captures CO₂ from ambient air using reusable solid sorbents and delivers it directly into alkaline cultivation media to support the growth of cyanobacteria, from laboratory flasks to outdoor raceway ponds. While long-term operation revealed challenges including biofouling and sorbent degradation, the results suggest that with improved sorbent durability, this approach could provide a scalable source of atmospheric carbon for producing sustainable fuels, proteins, natural colorants, and other bioproducts.

09 BIOMASS FUELS↗
NASA NTRS1976

Georgia Institute of Technology research on the Gas Core Actinide Transmutation Reactor (GCATR)

The program reviewed is a study of the feasibility, design, and optimization of the GCATR. The program is designed to take advantage of initial results and to continue work carried out on the Gas Core Breeder Reactor. The program complements NASA's program of developing UF6 fueled cavity reactors for power, nuclear pumped lasers, and other advanced technology applications. The program comprises: (1) General Studies--Parametric survey calculations performed to examine the effects of reactor spectrum and flux level on the actinide transmutation for GCATR conditions. The sensitivity of the results to neutron cross sections are to be assessed. Specifically, the parametric calculations of the actinide transmutation are to include the mass, isotope composition, fission and capture rates, reactivity effects, and neutron activity of recycled actinides. (2) GCATR Design Studies--This task is a major thrust of the proposed research program. Several subtasks are considered: optimization criteria studies of the blanket and fuel reprocessing, the actinide insertion and recirculation system, and the system integration. A brief review of the background of the GCATR and ongoing research is presented.

Clement, J. D.↗
DOE OSTI2026

INL Intern Poster Session

Characterization of off-gas constituents from nuclear fuel reprocessing can be measured using a residual gas analyzer. Characterization of this off-gas is important in a closed fuel cycle, where gasses such as Nox, Kr, I, and C-14 need to be removed from reprocessing plants to meet regulatory requirements. Both Kr and Xe have low chemical reactivity, making capture and separation difficult. Solid sorbents can be used to capture these gases as an alternative to cryogenic distillation, which is energy intensive and hazardous. AgZ-PAN and HZ-PAN are two solid sorbents that have demonstrated selective capture of Xe and Kr. A residual gas analyzer can be used to obtain breakthrough curves that demonstrate how well this adsorption and separation occur. The breakthrough curve is dependent on packing density, column size, and flow rate. Data obtained from the RGA was verified with a gas chromatographer.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Deep Learning Potential For Investigation of Chemical Conversion of CO2 at Air-Reactive Deep Eutectic Solvent Interface

Capturing CO2 from air is urgent to battle against the climate change. Traditional CO2 capture by alkaline solution or aqueous amine has high regeneration cost, equipment corrosion, and amine leakage. Deep eutectic solvents (DESs) are promising alternatives with low corrosion, non-toxicity, and biodegradable nature. Functionalized DESs can capture and convert CO2 at low partial pressures. Developing reactive DESs for efficient CO2 capture needs a foundational understanding of the reaction-transport coupling of CO2 at the air-DES interface. In this study, we develop a deep learning potential (DLP) to investigate the absorption and reaction of CO2 at the air-DES interface (DES: 1-ethyl-3-methylimidazolium 2-cyanopyrrolide ([Emim][2-CNpyr]) and ethylene glycol (EG)). The DLP model allows us to simulate chemical reactions at a lower computational cost with ab initio accuracy. By analyzing reaction free energy surfaces, molecular interactions among CO2, DES components and reaction products, and transport of CO2 through the interface, we identify three main reaction pathways of CO2 at the interface: forming carboxylate with [Emim], carbamate with [2-CNpyr], and carbonate with EG. The mechanistic understanding of CO2 chemisorption at the interface will facilitate the development of novel direct air capture technology using DESs.

Nguyen, Manh Tien↗