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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Acetylene Semi-Hydrogenation on a Perovskite Oxyhydride Surface: Insights from First Principles and Microkinetic Modeling

Although perovskite oxyhydrides (POHs) have shown promise as a support for selective hydrogenation, it is unknown if they themselves can catalyze alkyne semi-hydrogenation. Here, we use first-principles density functional theory, coupled with microkinetic modeling, to investigate acetylene semi-hydrogenation on a prototypical POH, cubic BaTiO 2.5 H 0.5 (BTOH). Two different mechanisms are examined on a representative surface of BTOH under the reaction conditions: both are based on the Horiuti–Polanyi mechanism, but the way of H 2 dissociation is different. In mechanism 1, a lattice hydride H atom and then a surface adsorbed H atom sequentially hydrogenate the adsorbed acetylene. In mechanism 2, two lattice hydride H atoms from the BTOH sequentially hydrogenate the adsorbed acetylene. In both mechanisms, the H atoms are replenished from gas phase H 2 dissociation. Using density functional theory (DFT), we have calculated pathways for these two mechanisms in hydrogenation of acetylene to ethylene, as well as further to ethane. Microkinetic modeling based on the DFT energetics indicates that at 523 K, hydrogenation to ethylene and ethane via mechanism 1 occurs at a rate up to two orders of magnitude faster than via mechanism 2. A selectivity analysis for the temperature range of 373–673 K shows that the product observed is essentially only ethylene within the more active mechanism 1. This is because at the steady state, there is a significant amount of surface anion vacancies that facilitate heterolytic H 2 dissociation and help stabilize a vinyl intermediate. In conclusion, the present findings suggest that POHs are capable of selective hydrogenation, thanks to their rich hydrogen surface-redox chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Re-evaluation of rate constants for the reaction N 2 H 4 (+ M) $^→_←$ NH 2 + NH 2 (+ M)

Rate constants for the dissociation/recombination reaction N 2 H 4 (+ M) $^→_←$ NH 2 + NH 2 (+ M) are determined by a combination of quantum-chemical calculations and statistical unimolecular rate theory. Between 1100 and 2500 K, limiting low-pressure rate constants for hydrazine dissociation in the bath gas Ar of k 0 = [Ar] 6.1 × 10 20 (T/1000 K) –7.3 exp (-34490 K/T) cm 3 mol –1 s –1 , limiting high-pressure rate constants of k ∞ = 7.6 × 10 16 (T/1000 K) –1.0 exp(-33600 K/T) s –1 , and center broadening factors of the falloff curves (between 1100 and 1600 K in Ar) of F cent = 0.71 exp(- T/1460 K) + 0.29 exp(- T/21 K) + exp(-13400 K/T) were calculated. Using equilibrium constants K C = 1.7 × 10 3 (T/1000 K) –1.5 exp(-33,460 K/T) mol cm –3 , between 300 and 600 K limiting low-pressure rate constants for the reverse recombination of NH 2 radicals in the bath gas N 2 of k rec,0 = [N 2 ] 4.4 × 10 20 (T/400 K) –6.9 exp (-1630 K/T) cm 6 mol –2 s –1 , limiting high-pressure rate constants of k rec,∞ = 4.4 × 10 13 (T/1000 K) 0.44 exp(-140 K/T) cm 3 mol -1 s –1 , and center broadening factors (between 300 and 600 K in N 2 ) of F cent = exp(- T/1130 K) + exp (-10340 K/T) were obtained. A comparison with experimental results for hydrazine dissociation from the literature suggests incomplete falloff extrapolations toward k ∞ and experimental problems in the determination of k 0 at temperatures above about 1600 K. Finally, implications of the present re-evaluated rate constants for the modeling of high temperature ammonia oxidation kinetics are discussed, showing an only small influence of their precise values on the overall properties of the process.

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

Three-Dimensional Free Gas Flow Focuses Basin-Wide Microbial Methane to Concentrated Methane Hydrate Reservoirs in Geological System

Here, we present a systematic model that links the generation, migration, phase partitioning, and accumulation of methane into a closed loop as the sediment is deposited from the seafloor and buried through the base of hydrate stability zone (BHSZ). In our model, methane is generated by biodegradation of organic carbon in muds. Hydrate does not form and methane is not trapped until a coarse-grained layer is deposited, because the small pores prevent hydrate formation in muds. Instead, methane diffuses into sands/silts where methane solidifies into hydrate. As hydrate-bearing sands/silts pass through the BHSZ during sediment burial, methane hydrate dissociates, and releases free gas. The released and the newly generated free gas below the BHSZ concentrates into a vertical/dipping zone with low capillary entry pressure and high permeability and flows upward driven its buoyancy. When free gas reaches the hydrate stability zone (HSZ), capillary forces drive free gas to flow laterally, preferentially enter sands/silts, feed hydrate growth, and elevate hydrate saturation. With three-dimensional focused free gas flow, microbial methane that is generated from a much larger fetch area of the entire basin, both above and below the BHSZ, is concentrated into coarse-grained layers at structural closures for hydrate formation. Our model illustrates how geological evolution, microbial methane generation, and gas flow by buoyancy couple to generate concentrated hydrate deposits in geological system. These insights can be used to explore for high-concentration methane hydrate and are important for understanding the methane budget and carbon cycle under the seafloor.

58 GEOSCIENCES↗
DOE OSTI2020

Cooperative Research and Development Agreement between National Energy Technology Laboratory and Korea Institute of Energy Research (KIER) [Abstract]

KIER and NETL will collaborate to study hydrate-based technologies to enhance desalination, gas separation, and hydrocarbon flow through pipelines and wellbores. With optimized selections of hydrate formers and reactors, gas hydrates can be effective and economic mechanisms of separation for solid-water and gas mixtures, and gas hydrate formation or dissociation can be significantly delayed or expedited with suitably selected additives. Comprehensive laboratory studies, including identifying novel hydrate formers or inhibitors to control temperature and pressure requirements and understanding their working mechanism or developing reactor systems for production of large quantities of hydrates, will be performed at both KIER and NETL either parallelly or serially.

03 NATURAL GAS↗
DOE OSTI2020

Cooperative Research and Development Agreement between National Energy Technology Laboratory and Raytheon Technologies Corporation [Abstract]

KIER and NETL will collaborate to study hydrate-based technologies to enhance desalination, gas separation, and hydrocarbon flow through pipelines and wellbores. With optimized selections of hydrate formers and reactors, gas hydrates can be effective and economic mechanisms of separation for solid-water and gas mixtures, and gas hydrate formation or dissociation can be significantly delayed or expedited with suitably selected additives. Comprehensive laboratory studies, including identifying novel hydrate formers or inhibitors to control temperature and pressure requirements and understanding their working mechanism or developing reactor systems for production of large quantities of hydrates, will be performed at both KIER and NETL either parallelly or serially.

02 PETROLEUM↗
DOE OSTI2023

2023 American Society for Mass Spectrometry (ASMS) 71st Annual Conference on Mass Spectrometry and Allied Topics

Title (20 words): The investigation of the mechanism for the water splitting by holmium oxide nitrate complex in gas-phase Introduction (120 words): The studies for hydrogen from water splitting is important for clean energy economy as molecular hydrogen is a potential energy carrier. Therefore, understanding the fundamental chemistry of water splitting is essential. The water splitting activated by [Ho(NO3)4]- was previously studied. The suggested mechanism was to first eliminate •NO2 from [Ho(NO3)4]- to make [HoO(NO3)3]-. Then, water was added to form [HoO(NO3)3(H2O)]-, followed by eliminating the •OH to form [HoOH(NO3)3]-. However, we proposed a new mechanism with the formation of [Ho(NO3)3]- prior to the water addition. Once water is added to this intermediate to make [Ho(NO3)3(H2O)]-, the •H is eliminated to form [HoOH(NO3)3]-. Here we have used a labeled experiments with 18-O nitrates. The results to support the new mechanism are discussed.

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

Activation, Dehydrogenation, and Carbon–Carbon Coupling of Methane by Iridium Cations Studied by Infrared Multiple Photon Dissociation Spectroscopy and Density Functional Theory

Products resulting from the sequential activation of one, two, three, and four methane molecules by atomic iridium cations were characterized by gas-phase infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. Iridium cations were generated using a laser ablation source and reacted with methane in a linear radiofrequency ion trap before mass analysis and spectroscopic interrogation in a Fourier transform ion cyclotron resonance mass spectrometer coupled to the free-electron laser for intracavity experiments (FELICE) beamline. Product ions were irradiated using infrared light over the 250–1500 cm –1 range. Comparisons between the experimental and DFT-calculated spectra enabled structural determination of the products formed. The observed products include HIrCH + , Ir(CH 2 ) 2 + , H s Ir(C 3 H 5 ) + , and Ir(CH 3 ) s (C 3 H 5 ) + , where the subscript s denotes a syn orientation of the two ligands. Furthermore, formation of the latter two products provides evidence for efficient C–H bond activation and subsequent C–C coupling on the atomic iridium cation.

Chemical reactions↗
DOE OSTI2021

Parabolic oxidation kinetics of a plutonium alloy at room temperature

Auger electron spectroscopy (AES) was used to characterize the oxide scale formed on an ~0.5 wt. % Ga plutonium metal alloy. Analysis of changes to the characteristic Auger transitions for Pu and O during sputter depth profiles were used in combination with previously measured sputter yields to determine the thickness of the oxide scale and provide insight into its chemistry. From this data, the parabolic kinetics for the Pu-Ga alloy were determined as a function of relative humidity, RH = 14–92%, and oxygen partial pressure, p(O 2 ) = 31–157 Torr, at 25°C. For each relative humidity investigated, the parabolic rate constant was found to be independent of oxygen partial pressure. Furthermore, power-law fits to the relative humidity effect on the rate constant was found to have a power of n = 1.265, indicating the diffusion species which rate-limits the reaction isn’t molecular water, which subsequent dissociates at the oxide-metal interface, or hydroxyl from dissociation at the gas-surface interface.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Gas Production from Hot Water Circulation through Hydraulic Fractures in Methane Hydrate-Bearing Sediments: THC-Coupled Simulation of Production Mechanisms

Methane hydrates, widely found in permafrost and deep marine sediments, have great potential as a future energy 6 source. Conventional production schemes perform poorly for challenging hydrate reservoirs with low permeability. We propose an 7 efficient production scheme by combining hydraulic fracturing from horizontal wells and hot water circulation through fractures. A 8 fully coupled thermo-hydro-chemical (THC) model is developed to simulate the key physical processes during gas production from 9 a hydrate reservoir representative of typical geological settings in Shenhu, South China Sea. We found that the gas production 10 process has two distinct stages divided by thermal breakthrough: a relatively short prebreakthrough stage and a postbreakthrough 11 stage yielding stable gas production. Heat advection along and near the hydraulic fracture dominates the prebreakthrough stage, 12 whereas conduction-driven thermal recovery in the volume around fractures dominates the postbreakthrough stage. We identified 13 that the steady-state injection temperature has a strong effect on the performance of the proposed scheme while the fluid mass 14 circulation rate has a moderate impact beyond a threshold. The proposed scheme proves to be efficient and robust over a range of 15 reservoir conditions with respect to initial hydrate saturation and intrinsic permeability, including their spatial heterogeneities, 16 thereby offering a promising solution for challenging reservoir conditions.

gas hydrate, fracture flow, gas production, numeri↗
DOE OSTI2022

Representations and strategies for transferable machine learning improve model performance in chemical discovery

Strategies for machine-learning (ML)-accelerated discovery that are general across material composition spaces are essential, but demonstrations of ML have been primarily limited to narrow composition variations. By addressing the scarcity of data in promising regions of chemical space for challenging targets such as open-shell transition-metal complexes, general representations and transferable ML models that leverage known relationships in existing data will accelerate discovery. Over a large set (~1000) of isovalent transition-metal complexes, we quantify evident relationships for different properties (i.e., spin-splitting and ligand dissociation) between rows of the Periodic Table (i.e., 3d/4d metals and 2p/3p ligands). We demonstrate an extension to the graph-based revised autocorrelation (RAC) representation (i.e., eRAC) that incorporates the group number alongside the nuclear charge heuristic that otherwise overestimates dissimilarity of isovalent complexes. To address the common challenge of discovery in a new space where data are limited, we introduce a transfer learning approach in which we seed models trained on a large amount of data from one row of the Periodic Table with a small number of data points from the additional row. We demonstrate the synergistic value of the eRACs alongside this transfer learning strategy to consistently improve model performance. Analysis of these models highlights how the approach succeeds by reordering the distances between complexes to be more consistent with the Periodic Table, a property we expect to be broadly useful for other material domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Breaking covalent bonds in the context of the many-body expansion (MBE). I. The purported “first row anomaly” in XH n (X = C, Si, Ge, Sn; n = 1–4)

We present a new, novel implementation of the Many-Body Expansion (MBE) to account for the breaking of covalent bonds, thus extending the range of applications from its previous popular usage in the breaking of hydrogen bonds in clusters to molecules. A central concept of the new implementation is the in situ atomic electronic state of an atom in a molecule that casts the one-body term as the energy required to promote it to that state from its ground state. The rest of the terms correspond to the individual diatomic, triatomic, etc., fragments. Its application to the atomization energies of the XH n series, X = C, Si, Ge, Sn and n = 1–4, suggests that the (negative, stabilizing) 2-B is by far the largest term in the MBE with the higher order terms oscillating between positive and negative values and decreasing dramatically in size with increasing rank of the expansion. The analysis offers an alternative explanation for the purported “first row anomaly” in the incremental H n–1 X–H bond energies seen when these energies are evaluated with respect to the lowest energy among the states of the XH n molecules. Due to the “flipping” of the ground/first excited state between CH 2 ( 3 B 1 ground state, 1 A 1 first excited state) and XH 2 , X = Si, Ge, Sn ( 1 A 1 ground state, 3 B 1 first excited state), the overall picture does not exhibit a “first row anomaly” when the incremental bond energies are evaluated with respect to the molecular states having the same in situ atomic states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Single-beam plasma source deposition of carbon thin films

A single-beam plasma source was developed and used to deposit hydrogenated amorphous carbon (a-C:H) thin films at room temperature. The plasma source was excited by a combined radio frequency and direct current power, which resulted in tunable ion energy over a wide range. The plasma source could effectively dissociate the source hydrocarbon gas and simultaneously emit an ion beam to interact with the deposited film. Using this plasma source and a mixture of argon and C 2 H 2 gas, a-C:H films were deposited at a rate of ~26 nm/min. The resulting a-C:H film of 1.2 µm thick was still highly transparent with a transmittance of over 90% in the infrared range and an optical bandgap of 2.04 eV. Young’s modulus of the a-C:H film was ~80 GPa. The combination of the low-temperature high-rate deposition of transparent a-C:H films with moderately high Young’s modulus makes the single-beam plasma source attractive for many coatings applications, especially in which heat-sensitive and soft materials are involved. Here, the single-beam plasma source can be configured into a linear structure, which could be used for large-area coatings.

14 SOLAR ENERGY↗
DOE OSTI2024

Predissociation-based measurements of bond dissociation energies: US 2 , OUS, and USe

The uranium-containing molecules US 2 , OUS, and USe have been investigated using a pulsed laser ablation supersonic beam molecular source with time-of-flight mass spectrometric detection. Spectra have been recorded using the resonant two-photon ionization method over the spectroscopic range from 277 to 238 nm. These species have a myriad of excited electronic states in this spectroscopic region, leading to spectra that are highly congested and appear quasicontinuous. Sharp predissociation thresholds are observed, allowing precise bond dissociation energies to be measured. In the case of the triatomic molecules, it was necessary to use one laser for excitation and a delayed laser for ionization in order to observe a sharp predissociation threshold that allowed a precise bond dissociation energy to be measured. The resulting thermochemical values are D 0 (SU-S) = 4.910 ± 0.003 eV, D 0 (OU-S) = 5.035 ± 0.004 eV, and D 0 (USe) = 4.609 ± 0.009 eV. These results provide the first measurement of D 0 (USe) and reduce the error limits in the previous values of D 0 (SU-S) and D 0 (OU-S) by a factor of more than 70.

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

YbH + formation in an ytterbium ion trap

The trapped 171 Yb + ion is a promising candidate for portable atomic clock applications. However, with buffer-gas cooled ytterbium ions, the ions can be pumped into a low-lying 2 F 7 / 2 state or form YbH + molecules. These dark states reduce the fluorescence signal from the ions and can degrade the clock stability. In this work, we study the dynamics of the populations of the 2 F 7 / 2 state and YbH + molecules under different operating conditions of our 171 Yb + ion system. Our study indicates that 2 F 7 / 2 -state ions can form YbH + molecules through interactions with hydrogen gas. As observed previously, dissociation of YbH + is observed at wavelengths around 369 nm. We also demonstrate YbH+ dissociation using 405 nm light. Moreover, we show that the population in the dark states can be limited by using a single repump laser at 935 nm. Our study provides insights into the molecular formation in a trapped ion system.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

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

Gas-Phase Stability of Large Lanthanide:Ligand Clusters Evaluated Using Collision-Induced Dissociation

Introduction In the reprocessing of f-elements present in used nuclear fuels, a variety of diglycolamides (DGA’s) are used as extractants for actinide partitioning. In particular, the Actinide-Lanthanide Separation (ALSEP) process typically utilizes either the N,N,N’,N’-tetraoctyl diglycolamide (TODGA) or N,N,N',N'-tetra-2-ethylhexyl diglycolamide (T2EHDGA) extractant ligands following the partitioning of uranium and plutonium from used nuclear fuel. To better understand fundamental interactions in these processes, covalent bonding of several f-elements with diglycolamides, primarily TODGA, is investigated in the gas phase using nanospray ionization and a quadrupole time-of-flight mass spectrometer. Further, analysis of the identity and relative strength of the cluster is enabled by MS2 isolation and collision induced dissociation. Methods Metal ion cluster analysis was completed using a Bruker (Billerica, MA, USA) mircOTOF-Q II quadrupole time-of-flight mass spectrometer with a CaptiveSpray nanospray ion source. Detection was accomplished using positive ionization mode. Metal: ligand solutions were assembled as 30 µM europium nitrate, samarium nitrate, cerium nitrate, or holmium nitrate and 3 µM DGA in acetonitrile or a 50:50 mixture of acetonitrile: isopropanol. Preliminary data The samarium cluster experiments yielded clusters with a samarium:TODGA ratio of up to 1:7 able to be isolated and evidence of greater ratios present in the mass spectrum. This is surprising, as metal clusters are not expected to have a coordination space able to accommodate this many TODGA ligands, due to its size and tridenticity. Collisional activation of [Sm(TODGA)3]3+ suggested loss of a TODGA radical cation, in addition to ligand fragmentation. In contrast, activation of clusters with higher Sm:TODGA ratios resulted in loss of entire ligands, with no evidence of fragmentation. A lower collision energy was required to remove ligands as the number of bound TODGAs increased, suggesting that in larger clusters, ligands are more delicately complexed to the metal. In addition, several clusters were observed with the composition [Sm(NO3)x(TODGA)n x]+3 x. With a single nitrate ion, clusters with up to six TODGAs were able to be isolated. In a similar pattern to the samarium clusters containing only TODGA, less collision energy was required to eliminate one or more TODGAs with increasing size. Clusters with composition [Sm(NO3)(TODGA)n-1]2+ appeared in lower abundance and were more collisionally stable than [Sm(TODGA)n]3+ clusters. With two nitrate ions, only clusters with a single TODGA were able to be isolated. Analogous europium experiments resulted in similar clusters. Ratios of up to 1:7 Eu:TODGA and clusters with one nitrate and up to five TODGAs were isolated. In clusters with two nitrate ions, only one or two TODGAs were observed to be bound. Similar to samarium, MS2 experiments with the Eu clusters suggested that larger clusters required less collision energy to eliminate TODGA. Europium clusters with the composition [Eu(NO3)(TODGA)n-1]2+ were observed in greater abundance and with greater stability than the equivalent cluster with the composition [Eu(TODGA)n]3+. Novel Aspect These are the first reported Ln:TODGA clusters, allowing us to begin to investigate intrinsic complexation of lanthanides with process-relevant ligands.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗