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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

A Closer Look at Fe(II) Passivation of Goethite

Our understanding of how Fe(II) reacts with Fe(III) oxides has evolved significantly based on evidence for electron transfer at the oxide-water interface and Fe(II)-catalyzed recrystallization. Recent experiments, as well as computational calculations, further suggest that defects at oxide surfaces can facilitate electron transfer. There is, however, some evidence that these processes cease after continued contact with Fe(II). Here, we explore the sustainability of these processes over longer time frames by measuring whether exposure to Fe(II) inhibits Fe(II)-goethite electron transfer, and whether this inhibition is reversible. To quantify the extent of electron transfer, we used selective isotope labeling with 57Fe Mössbauer spectroscopy. The results revealed that pre-reacting goethite with Fe(II) decreases the extent of electron transfer during subsequent exposures, and that less electron transfer occurs with increasing reaction time. Similarly, X-ray absorption spectroscopy and magnetic circular dichroism suggest that reaction with Fe(II) consumes surface defects and forms a passivation layer, making goethite less susceptible to electron transfer. When Fe(II) is removed by either wet chemical extraction or oxidation, electron transfer is mostly restored, suggesting that inhibition of electron transfer is reversible. Our results show that in environmental systems, which are commonly subjected to transient geochemical fluctuations, electron transfer between Fe(II) and Fe oxides, and processes linked to it, are likely to be relevant beyond just short time scales.

Andrade de Notini, Luiza↗
DOE OSTI2022

A Water-Resistant Hydrogen-Bonded Organic Framework for Ethane/Ethylene Separation in Humid Environments

The separation of ethane (C 2 H 6 ) and ethylene (C 2 H 4 ) represents a crucial process for the production of polymer-grade C 2 H 4 , and adsorptive separation holds enormous promise for this industrially important but challenging task. Furthermore we report a new hydrogen-bonded organic frameworks (HIAM-102) with suitable channel and superhydrophobicity for preferential adsorption of C 2 H 6 over C 2 H 4 . HIAM-102 shows a C 2 H 6 /C 2 H 4 IAST selectivity of 1.9 and C 2 H 6 uptake of 48.25 cm 3 /g at 1 bar and 298 K. Benefitted from the hydrophobic pore surface, it can well-separate C 2 H 6 and C 2 H 4 under highly humid conditions as confirmed by experimental column breakthrough measurements. Computational calculations provide additional support for the experimental observations that the nonpolar channel of HIAM-102 interact favorably with C 2 H 6 over C 2 H 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Demonstration of Selective Single-Barium Ion Detection with Dry Diazacrown Ether Naphthalimide Turn-on Chemosensors

Single-molecule fluorescence imaging (SMFI) of gas-phase ions has been proposed for “barium tagging,” a burgeoning area of research in particle physics to detect individual barium daughter ions. This has potential to significantly enhance the sensitivity of searches for neutrinoless double-beta decay (0νββ) that is obscured by background radiation events. The chemistry required to make such sensitive detection of Ba 2+ by SMFI in dry Xe gas at solid interfaces has implications for solid-phase detection methods but has not been demonstrated. Here, we synthesized simple, robust, and effective Ba 2+ -selective chemosensors capable of function within ultrapure high-pressure 136 Xe gas. Turn-on fluorescent naphthalimide-(di)azacrown ether chemosensors were Ba 2+ -selective and achieved SMFI in a polyacrylamide matrix. Here, fluorescence and NMR experiments supported a photoinduced electron transfer mechanism for turn-on sensing. Ba 2+ selectivity was achieved with computational calculations correctly predicting the fluorescence responses of sensors to barium, mercury, and potassium ions. With these molecules, dry-phase single-Ba 2+ ion imaging with turn-on fluorescence was realized using an oil-free microscopy technique for the first time—a significant advance toward single-Ba 2+ ion detection within large volumes of 136 Xe, plausibly enabling a background-independent technique to search for the hypothetical process of 0νββ.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Splitting Mono- and Di-Branched Alkane Isomers by a Robust Aluminum-Based Metal-Organic Framework Material with Optimal Pore Dimensions

The separation of alkanes with different degrees of branching, particularly mono- and dibranched isomers, represents a challenging yet important industrial process for the production of premium gasoline blending components with high octane number. We report here the separation of linear/monobranched and dibranched alkanes through complete molecular sieving by a robust aluminum-based MOF material, Al-bttotb (H 3 bttotb = 4,4',4"-(benzene-1,3,5-triyltris(oxy))tribenzoicacid). Single- and multicomponent adsorption experiments reveal that the material adsorbs linear and monobranched alkanes, but fully excludes their dibranched isomers. Adsorption sites of alkanes within the MOF channels have been identified by single-crystal X-ray diffraction studies, and the adsorption mechanism was explored through computational calculations and modeling. The highly selective adsorption of the MOF should be attributed to its optimal pore dimensions.

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

Proton, Electron, and Hydrogen-Atom Transfer Thermodynamics of the Metal–Organic Framework, Ti-MIL-125, Are Intrinsically Correlated to the Structural Disorder

Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine catalytically relevant charge transfer thermodynamics. The Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 nodes structurally mimic TiO 2 , which has shown some PCET reactivity toward reactions of H 2 , O 2 , and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential (E OCP ) measurements, we have determined that all crystallites undergo a 1H + /1e – redox reaction, which, given the stoichiometry, can be considered as a net H atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti 3+ O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induced more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the “missing-linker” defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using pK a or band gaps (E g ), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered “true” single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO 2 and other redox-active MOFs.

Bond dissociation free energy↗
DOE OSTI2020

How Rh surface breaks CO 2 molecules under ambient pressure

Utilization of carbon dioxide (CO 2 ) molecules leads to increased interest in the sustainable synthesis of methane (CH 4 ) or methanol (CH 3 OH). The representative reaction intermediate consisting of a carbonyl or formate group determines yields of the fuel source during catalytic reactions. However, their selective initial surface reaction processes have been assumed without a fundamental understanding at the molecular level. Here, we report direct observations of spontaneous CO 2 dissociation over the model rhodium (Rh) catalyst at 0.1 mbar CO 2 . The linear geometry of CO 2 gas molecules turns into a chemically active bent-structure at the interface, which allows non-uniform charge transfers between chemisorbed CO 2 and surface Rh atoms. By combining scanning tunneling microscopy, X-ray photoelectron spectroscopy at near-ambient pressure, and computational calculations, we reveal strong evidence for chemical bond cleavage of O-CO* with ordered intermediates structure formation of (2 × 2)-CO on an atomically flat Rh(111) surface at room temperature.

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

Neighboring Pd single atoms surpass isolated single atoms for selective hydrodehalogenation catalysis

Single atom catalysts have been found to exhibit superior selectivity over nanoparticulate catalysts for catalytic reactions such as hydrogenation due to their single-site nature. However, improved selectively is often accompanied by loss of activity and slow kinetics. Here we demonstrate that neighboring Pd single atom catalysts retain the high selectivity merit of sparsely isolated single atom catalysts, while the cooperative interactions between neighboring atoms greatly enhance the activity for hydrogenation of carbon-halogen bonds. Experimental results and computational calculations suggest that neighboring Pd atoms work in synergy to lower the energy of key meta-stable reactions steps, i.e., initial water desorption and final hydrogenated product desorption. The placement of neighboring Pd atoms also contribute to nearly exclusive hydrogenation of carbon-chlorine bond without altering any other bonds in organohalogens. The promising hydrogenation performance achieved by neighboring single atoms sheds light on a new approach for manipulating the activity and selectivity of single atom catalysts that are increasingly studied in multiple applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Characterization of the high-pressure and high-temperature phase diagram and equation of state of chromium

The high-pressure and high-temperature phase diagram of chromium has been investigated both experimentally (in situ), using a laser-heated diamond-anvil cell technique coupled with synchrotron powder X-ray diffraction, and theoretically, using ab initio density-functional theory simulations. In the pressure–temperature range covered experimentally (up to 90 GPa and 4500 K, respectively) only the solid body-centred-cubic and liquid phases of chromium have been observed. Experiments and computer calculations give melting curves in agreement with each other that can both be described by the Simon–Glatzel equation $T_{m}(P) = 2136K (1 + P/25.9)^{0.41}$ In addition, a quasi-hydrostatic equation of state at ambient temperature has been experimentally characterized up to 131 GPa and compared with the present simulations. Both methods give very similar third-order Birch–Murnaghan equations of state with bulk moduli of 182–185 GPa and respective pressure derivatives of 4.74–5.15. According to the present calculations, the obtained melting curve and equation of state are valid up to at least 815 GPa, at which pressure the melting temperature is 9310 K. Finally, from the obtained results, it was possible to determine a thermal equation of state of chromium valid up to 65 GPa and 2100 K.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spectroscopic characterization of a new Re(i) tricarbonyl complex with a thiosemicarbazone derivative: towards sensing and electrocatalytic applications

This work describes the preparation of a new thiosemicarbazone derivative, (Z)- N -ethyl-2-(6-oxo-1,10-phenanthrolin-5(6 H )-ylidene)hydrazinecarbothioamide (phet) and its respective Re( I ) tricarbonyl chloro complex, fac -[ReCl(CO) 3 (phet)]. The spectroscopic, photophysical and electrochemical properties of the new complex were fully investigated through steady state and time-resolved techniques along with computational calculations. In fac -[ReCl(CO) 3 (phet)], the new ligand is coordinated to the metal center through the pyridyl rings of the phenanthroline moiety. The unbound electron pairs in the S atom of the bending thiosemicarbazone group induce new low energy lying electronic transitions. Consequently, enhanced visible light absorption up to 550 nm is observed in acetonitrile due to the overlap between MLCT Re→phet and IL phet(n→π*) transitions. The absorption bands and emission quantum yields of fac -[ReCl(CO) 3 (phet)] are sensitive to proton concentration due to an acid-basic equilibrium in the N atoms of the thiosemicarbazone. Proton dissociation constants of 10.0 ± 0.1 and 11.4 ± 0.2 were determined respectively for the ground and excited states of the new complex. Spectral changes could also be observed in the presence of Zn 2+ cations which can be further explored for sensing applications. The electrochemical behavior of the new complex was studied in detail, revealing up to four one electron reduction processes in the range from 0 to -2.4 V vs. Fc + /Fc. With support of DFT calculations, the first three processes are ascribed to the reduction of the coordinated phet ligand followed by the Re I/0 reduction and consequent Cl - release. Furthermore, the new complex was able to act as an electrocatalyst for CO 2 reduction into CO ( E onset = -1.92 V vs. Fc + /Fc), with a turnover frequency of 2.81 s -1 and turnover number of 24 ± 1 in anhydrous acetonitrile, being the first Re( I ) tricarbonyl complex with a thiosemicarbazone derivative described for this goal. The detailed characterization carried out here can drive the development of new Re( I )-thiosemicarbazone derivatives for different applications.

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

Kinetics and mechanisms of polycondensation reactions between aryl halides and bisphenol A

Aryl chlorides (ArCl) or aryl fluorides (ArF) were used in polycondensation reactions to form poly(arylene ether sulfone)s (PAES). Interestingly, the kinetics of the ArF reaction fit a third-order rate law, which is attributed to the activation of the carbon–fluorine bond by two potassium cations (at least one bound to phenolate), which form a three-body complex. Here, the ArCl monomer follows a second-order rate law, where a two-body complex forms at the initial state of the aromatic nucleophilic substitution (S N Ar) pathway. These metal cation-activated complexes act as intermediates during the attack by the nucleophile. This finding was reproduced with either the potassium or the sodium counterion (introduced via potassium carbonate or sodium carbonate). Through a combination of experimental analysis of reaction kinetics and computational calculations with density functional theory (DFT) methods, the present work extends the fundamental understanding of polycondensation mechanisms for two aryl halides and highlights the importance of the CX–metal interaction(s) in the S N Ar reaction, which is translational to other ion-activated substitution reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Understanding the dopant induced effects on SFX-MeOTAD for perovskite solar cells: a spectroscopic and computational investigation

SFX-MeOTAD [2,2',7,7'-tetrakis(N,N-di(4-methoxyphenyl)amino)-spiro-(fluorene-9,9'-xanthene)] (also known as X60) has emerged as a cost-effective alternative to the ubiquitous, but excessively-expensive, spiro-MeOTAD hole transport material (HTM) in perovskite solar cells. Using its pre-oxidised dicationic salt, SFX-(TFSI) 2 , a controlled concentration dependent conductivity tuning of this HTM without the requirement of air (oxygen) exposure has been carried out. This study details the modifications in the optical and electrical properties of this low cost HTM as a function of the concentration of the dicationic salt (0–100 mol%) using UV-vis absorption and electrical conductivity measurements. X-ray absorption and photoelectron spectroscopy investigations have been carried out to elucidate the role of the dicationic salt in the enhanced electronic properties of SFX-MeOTAD. By incorporating the dicationic SFX-(TFSI) 2 it has been shown that the conductivity of SFX-MeOTAD increased by 4 orders of magnitude from 2.55 × 10 –8 S cm –1 to 9.4 × 10 –4 S cm –1 when using an optimal dopant concentration of 20.5 mol%. The degree of oxidation of SFX-MeOTAD was determined through UV-vis absorption and consolidated using the computational calculations. The XPS study reveals that doping SFX-MeOTAD with SFX(TFSI) 2 not only results in the oxidation of the HTM but also leads to a variation in the local chemistry around carbon and nitrogen which directly influences the conductivity of the doped films. NEXAFS studies indicate that doping enhances the aromatic nature of the molecule initially but increasing the dopant concentration further affects the aromaticity and possibly the π stacking, similar to the trend seen in dopant concentration dependent conductivity of the SFX-MeOTAD films. These findings have implications on the choice of dopant concentration and counterions more generally for triarylamine based HTMs.

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

KRUSTY Experiment: Reactivity Insertion Accident Analysis

The centerpiece of the Kilopower Project, i.e., the Kilowatt Reactor Using Stirling TechnologY (KRUSTY) test, consists of the development and testing of a ground technology demonstration of a small fission power system based on a 1-kW(electric) space science power requirement. The KRUSTY test was authorized by the U.S. Department of Energy’s (DOE’s) National Nuclear Security Administration Nevada Field Office. Authorization was obtained by adding an amendment to the existing regulatory documents for the National Criticality Experiments Research Center to cover the KRUSTY experiment. This amendment was reviewed and approved by the DOE. The most important safety question for the experiment was the addition of over 2 $ of excess reactivity to the reactor system. This amount of excess reactivity meant that the analyst could postulate accidents where the reactor went prompt critical, leading to physical shock or melting of the fuel. This paper analyzes these accidents using computer calculations and examines the controls used to mitigate them. The estimation of the impacts both on accident progression and consequences of reactivity insertion events was a significant part of obtaining approval for the KRUSTY experiment. The regulatory approval of KRUSTY was one of the first to be obtained for a completely new reactor concept in many decades.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2024

Monte Carlo Perturbation Analysis of Fuel Temperature Variations in the MCNP Model of the Annular Core Research Reactor

The Annular Core Research Reactor (ACRR) Monte Carlo N-Particle (MCNP) model is used by ACRR reactor operators and experiment designers at Sandia National Laboratories for a variety of computational calculations ranging from reactor kinetics parameter estimates and safety analyses to experimental planning. To understand the dominant source of uncertainty within the MCNP model, perturbations in temperature were applied to individual ACRR MCNP fuel rods. Fuel rod temperatures were randomly sampled from a uniform distribution from operational temperatures to quantify temperature-related uncertainty effects. Stochastic mixing was used to blend the cross sections of the desired temperatures using the MCNP continuous and Thermal Neutron Scattering Treatment [S(α,β)] libraries in ENDF/B-VII.1. Furthermore, this uncertainty analysis produced a 640 row × 640 column correlation and covariance matrix of the neutron energy spectra. Positive covariance was produced around the 1-MeV region and the 0.2-eV region. Correlation was found in the thermal and fast energy regions, but no correlation was observed in the slowing-down energy region because interactions in this region are not dominated by fuel.

ACRR↗
DOE OSTI2022

Editorial for focus on nanophase materials for next-generation lithium-ion batteries and beyond

Lithium-ion batteries (LIBs) have revolutionized our society in many respects, and we are expecting even more favorable changes in our lifestyles with newer battery technologies. In pursuing such eligible batteries, nanophase materials play some important roles in LIBs and beyond technologies. Here, stimulated by their beneficial effects of nanophase materials, we initiated this Focus. Excitingly, this Focus collects 13 excellent original research and review articles related to the applications of nanophase materials in various rechargeable batteries, ranging from nanostructured electrode materials, nanoscale interface tailoring, novel separators, computational calculations, and advanced characterizations.

25 ENERGY STORAGE↗
DOE OSTI2021

A Proxy Signature-Based Drone Authentication in 5G D2D Networks

5G is the beginning of a new era in cellular communication, bringing up a highly connected network with the incorporation of the Internet of Things (IoT). To flexibly operate all the IoT devices over a cellular network, Device-toDevice (D2D) communication standard was developed. However, IoT devices such as drones utilizing 5G D2D services could be a perfect target for malicious attacks as they pose several safety threats if they are compromised. Furthermore, there will be heavy traffic with an increased number of IoT devices connected to the 5G core. Therefore, we propose a lightweight, fast, and reliable authentication mechanism compatible with the 5G D2D ProSe standard mechanisms. Specifically, we propose a distributed authentication with a delegation-based scheme instead of the repeated access to the 5G core network key management functions. Hence, a legitimate drone is authorized by the core network via offering a proxy signature to authenticate itself to other drones. We implemented the proposed protocol in ns-3 that supports 5G D2D-based communication. We also conducted computational calculations on the RaspberryPi3 IoT device to mimic the drone calculation process and delays. The results demonstrate that the proposed protocol is lightweight and reliable

5G security↗