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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 1,063 records · Page 59

Amorphous-crystalline transition-driven synthesis of Co single-atom catalysts on MoO 3 for enhanced hydrogen evolution in acidic and alkaline media

Single atom catalysts (SACs) dispersed in metal oxide supports offer not only maximized catalyst utilization but also extended modulation capabilities through interactions between the SA and its support. However, achieving facile preparation and ensuring electrochemical durability of such SACs, particularly for hydrogen evolution reaction (HER) applications, remain formidable challenges. Here, our study addresses these issues by employing an amorphous-to-crystalline phase transition in MoO 3 to synthesize a cobalt (Co) SA catalyst. This method facilitates the production of highly selective SA catalysts at low temperatures and ensures their enhanced stability in HER applications. The Co SA MoO 3 catalyst exhibits superior performance in HER, operating effectively in both acidic and alkaline environments. Significantly, it maintains stable HER activity across these diverse electrolytic conditions. Our Density Functional Theory (DFT) calculations provide insights into the exceptional HER performance of Co SA MoO 3 . These calculations reveal that the strong affinity for hydrogen and water, facilitated by the modulation of the p-band orbitals at specific oxygen sites adjacent to the Co SA, establishes a thermoneutral pathway for HER. This study represents a pivotal advancement, showcasing a highly practical and robust single-atom catalyst, marking a significant stride towards sustainable energy solutions.

36 MATERIALS SCIENCE↗

Development of ceria-supported metal-oxide (MO x /CeO 2 ) catalysts via a one-pot chemical vapor deposition (OP-CVD) technique: Structure and reverse water gas shift reaction study

Current synthesis techniques for metal oxide (MO x )-supported catalysts have certain limitations of undesired target loading, ineffective dispersion of active species over the surface, uncontrolled particle size of active species, and complicated synthesis steps. Here, we developed a one-pot chemical vapor deposition (OP-CVD) methodology; by using which a solid metal precursor forms a vapor in a controlled condition and gets supported over the surrounding matrix. The theoretical stability followed by experimental validation using TGA is crucial for selecting the metal precursors. Three simple steps viz. premixing, dispersion, and rapid fixation by calcination are involved in the catalyst development via the OP-CVD approach. This study solely focused on the synthesis of 3d transition MO x over ceria support. The physicochemical characterizations of the prepared catalysts were performed by XRD, ICP-OES, SEM-EDX, CO pulse chemisorption, XANES, and EXAFS analyses to understand the crystal structure of involved species, target metal loading, dispersion, and particle size and prove the feasibility and viability of OP-CVD. The prepared catalysts were further tested for reverse water gas shift (RWGS) reaction to link their structural information with activity. The RWGS reaction data showed that the CO activity and CO selectivity were metal - and metal precursor-dependent. Higher CO activity of > 0.1 mol/h g-cat was observed for Cu and Co-based catalysts, with CO selectivity of ~100 %. This study provides an opportunity to produce efficient supported catalysts in a convenient way, providing effective catalytic activity.

36 MATERIALS SCIENCE↗

Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution

The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV-visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize U IV , generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize U IV to a lesser extent, as evidenced by the mix of U IV and U VI complexes observed via XAS. Finally, CV and SEC measurements confirmed that the U IV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and U VI ions can be reduced, likely proceeding via a two-electron reduction process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ketjenblack-Supported and Unsupported ZrO 2 –ZrN Nanoparticle Systems for Enabling Efficient Electrochemical Nitrogen Reduction to Ammonia

Artificial N 2 fixation via the electrocatalytic nitrogen (N 2 ) reduction reaction (NRR) has been recently promoted as a rational route toward reducing energy consumption and CO 2 emission as compared with the traditional Haber–Bosch process. Nevertheless, optimizing NRR relies on developing highly efficient electrocatalysts. Herein, we report on the reliable and reproducible synthesis of two promising electrocatalysts in either the presence or absence of Ketjenblack (KB), namely, ZrO 2 –ZrN@KB and ZrO 2 –ZrN systems, synthesized through the nitriding of Zr. Both materials had never previously been considered for NRR, to the best of our knowledge. Nevertheless, both of these electrocatalysts incorporated a combination of tetragonal ZrO 2 , ZrON, and cubic ZrN and showed excellent activity and durability toward NH 3 formation. Moreover, the maximum NH3 production rate of 84.1 μg h –1 mg –1 at -0.7 V vs a reversible hydrogen electrode (RHE) was achieved with the ZrO 2 –ZrN electrocatalyst with an impressive Faradaic efficiency of 21.2% at -0.6 V vs RHE, indicating a high selectivity associated with the NRR. Additionally, the catalysts demonstrated excellent stability during the electrolysis process and recycling tests. Here we postulate that the combination of exposed active sites of ZrN and ZrO 2 likely contributes to the enhanced NRR performance attributed to ZrO 2 –ZrN.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks

Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. In this work, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal–organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal–organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Lastly and most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

36 MATERIALS SCIENCE↗

Evaluating structure selection in the hydrothermal growth of FeS 2 pyrite and marcasite

While the ab initio prediction of the properties of solids and their optimization towards new proposed materials is becoming established, little predictive theory exists as to which metastable materials can be made and how, impeding their experimental realization. Here we propose a quasi-thermodynamic framework for predicting the hydrothermal synthetic accessibility of metastable materials and apply this model to understanding the phase selection between the pyrite and marcasite polymorphs of FeS 2 . We demonstrate that phase selection in this system can be explained by the surface stability of the two phases as a function of ambient pH within nano-size regimes relevant to nucleation. This result suggests that a first-principles understanding of nano-size phase stability in realistic synthesis environments can serve to explain or predict the synthetic accessibility of structural polymorphs, providing a guideline to experimental synthesis via efficient computational materials design.

36 MATERIALS SCIENCE↗

Formation mechanism of steep wave front in magnetized plasmas

Bifurcation from a streamer to a solitary drift wave is obtained in three dimensional simulation of resistive drift waves in cylindrical plasmas. The solitary drift wave is observed in the regime where the collisional transport is important as well as fluctuation induced transport. The solitary drift wave forms a steep wave front in the azimuthal direction. The phase of higher harmonic modes are locked to that of the fundamental mode, so that the steep wave front is sustained for a long time compared to the typical time scale of the drift wave oscillation. The phase entrainment between the fundamental and second harmonic modes is studied, and the azimuthal structure of the stationary solution is found to be characterized by a parameter which is determined by the deviation of the fluctuations from the Boltzmann relation. There are two solutions of the azimuthal structures, which have steep wave front facing forward and backward in the wave propagation direction, respectively. The selection criterion of these solutions is derived theoretically from the stability of the phase entrainment. The simulation result and experimental observations are found to be consistent with the theoretical prediction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

From binaries to multiples. II. Hierarchical multiplicity of F and G dwarfs

Statistics of hierarchical multiplicity among solar-type dwarfs are studied using the distance-limited sample of 4847 targets presented in the accompanying Paper I. Known facts about binaries (multiplicity fraction 0.46, lognormal period distribution with median period 100 yr and logarithmic dispersion 2.4, and nearly uniform mass-ratio distribution independent of the period) are confirmed with a high statistical significance. The fraction of hierarchies with three or more components is 0.13 ± 0.01, and the fractions of targets with n = 1, 2, 3, ... components are 54:33:8:4:1. Subsystems in the secondary components are almost as frequent as in the primary components, but in half of such cases both inner pairs are present. The high frequency of those 2+2 hierarchies (4%) suggests that both inner pairs were formed by a common process. The statistics of hierarchies can be reproduced by simulations, assuming that the field is a mixture coming from binary-rich and binary-poor environments. Periods of the outer and inner binaries are selected recursively from the same lognormal distribution, subject to the stability constraint and accounting for the correlation between inner subsystems. The simulator can be used to evaluate the frequency of multiple systems with specified parameters. However, it does not reproduce the observed excess of inner periods shorter than 10 days, caused by tidal evolution.

79 ASTRONOMY AND ASTROPHYSICS↗

Canted antiferromagnetic order in the monoaxial chiral magnets V 1/3 TaS 2 and V 1/3 NbS 2

The Dzyaloshinskii-Moriya (DM) interaction is present in the transition metal dichalcogenides (TMDC) magnets of form M 1 / 3 T S 2 ( M = 3 d transition metal, T ϵ { Nb , Ta } ), given that the intercalants M form 3 × 3 superlattices within the structure of the parent materials T S 2 and break the centrosymmetry. Competition between DM and ferromagnetic exchange interactions has been shown to stabilize a topological defect known as a chiral soliton in select intercalated TMDCs, initiating interest both in terms of fundamental physics and the potential for technological applications. In the current article we report on our study of the materials V 1 / 3 TaS 2 and V 1 / 3 NbS 2 , using a combination of x-ray powder diffraction, magnetization, and single crystal neutron diffraction. Historically identified as ferromagnets, our diffraction results instead reveal that vanadium spins in these compounds are arranged into an A-type antiferromagnetic configuration at low temperatures. Refined moments are 1.37(6) and 1.50(9) μ B for V 1 / 3 TaS 2 and V 1 / 3 NbS 2 , respectively. Transition temperatures T c = 32 K for V 1 / 3 TaS 2 and 50 K for V 1 / 3 NbS 2 are obtained from the magnetization and neutron diffraction results. We attribute the small net magnetization observed in the low-temperature phases to a subtle ( ~ 2 ° ) canting of XY spins in the out-of-plane direction. These new results are indicative of dominant antiferromagnetic exchange interactions between the vanadium moments in adjacent a b planes, likely eliminating the possibility of identifying stable chiral solitons in the current materials.

36 MATERIALS SCIENCE↗

A partial-volume correction for quantitative spectral x-ray radiography

The technique of spectral radiography has been shown to accurately discriminate a materials elemental composition by using known x-ray physics. This is achieved with a state-of-the-art pixelated spectrometer and a high-fidelity physical model. Similar to other radiographs, the system suffers from partial volume attenuation where the sample projection onto a pixel is only a fraction of the pixel area, leaving the rest unattenuated. This study updates the physical model to account for fractional area which presents new challenges to the existing algorithm. We present how this update is made and explore approaches to stabilize the algorithm through parameter scaling, constrained optimization, and hyperparameter selection.

Gillis, Wesley C.↗

Enabling Grid-Forming Control with Fault Ride-Through in Unbalanced Distribution Networks

Distribution networks are often unbalanced, causing oscillatory responses in inverter control designed for balanced conditions. Here, to address this problem, this paper proposes a novel time-domain transformation appropriate for inverter control and enables the decomposition of three-phase unbalanced signals into constant positive and negative components. Relations useful for calculating unbalanced active and reactive power are derived from first principle, providing insight into vector products of unbalanced three-phase signals. Furthermore, a grid-forming control effective under unbalanced conditions is developed, which delivers superior performance while meeting UNIFI1 specifications for grid-forming control under unbalanced conditions. specifications applicable to category 4 inverter-based resource, like setting and regulating frequency/voltage, providing voltage support, sharing active power, injecting negative sequence current, and riding through faults. A current limiter is proposed for safe fault ride-through and integrates with the grid-forming control featuring frequency/voltage droop controllers and current and voltage control loops. The transformation of interconnected inverters is formulated and stability of the proposed control analyzed to support robust parameter selections. The effectiveness of the proposed transformation and grid-forming control is demonstrated through analytical results and real-time simulation of a IEEE 123 distribution network on the Real-Time Digital Simulator. Comparison with existing methods shows that the proposed strategy satisfies the UNIFI specifications with a much better performance.

24 - POWER TRANSMISSION AND DISTRIBUTION↗

Contrast Matching Biopolymers: A SANS-Based Approach to Structural Characterization of Chitosan

Immobilizing enzymes in polysaccharide-based matrices has been shown to improve both their stability and their catalytic efficiency. Among available materials, chitosan was selected for its abundance, biocompatibility, and versatility in a range of applications. While the broader aim of this work is to study chitosan as a matrix for immobilizing carbonic anhydrase (CA) for CO₂ capture, this study focused on determining the contrast match point (CMP) of hydrogenated and deuterated chitosan in D₂O:H₂O mixtures to enable future structural investigations using small-angle neutron scattering (SANS). Previous work successfully synthesized deuterated chitosan from Rhizopus oryzae mycelia and assessed the degree of deuteration using Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Building on this foundation, the current study determined the CMPs of both H-chitosan and D-chitosan by performing SANS measurements across a range of D₂O:H₂O solvent contrasts. The extracted CMPs for both forms correlated well with their respective calculated scattering length densities (SLDs), validating the experimental approach. These results establish a critical reference for selective contrast matching in future SANS studies of carbonic anhydrase immobilized in chitosan matrices, enabling detailed structural analysis of enzyme–matrix interactions.

Kosgallana, Chathurika J [ORNL] (ORCID:00000002851↗

Plasmonics Based Harsh Environment Compatible Chemical Sensors

Au-YSZ, Au-TiO 2 and Au-CeO 2 nanocomposite films have been investigated as a potential sensing element for high-temperature plasmonic sensing of H 2 , CO, and NO 2 in an oxygen containing environment. The Au-YSZ and Au-TiO 2 films were deposited using PVD methods, while the CeO 2 thin film was deposited by molecular beam epitaxy (MBE) and Au was implanted into the as-grown film at an elevated temperature followed by high temperature annealing to form well-defined Au nanoclusters. Each of the films were characterized by x-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). For the gas sensing experiments, separate exposures to varying concentrations of H 2 , CO, and NO 2 were performed at a temperature of 500°C in oxygen backgrounds of 5.0, 10, and ~21% O 2 . Changes in the localized surface plasmon resonance (LSPR) absorption peak were monitored during gas exposures and are believed to be the result of oxidation-reduction processes that fill or create oxygen vacancies in the respective metal oxides. This process affects the LSPR peak position either by charge exchange with the Au nanoparticles or by changes in the dielectric constant surrounding the particles. Hyperspectral multivariate analysis was used to gauge the inherent selectivity of the film between the separate analytes. From principal component analysis (PCA), unique and identifiable responses were seen for each of the analytes. Linear discriminant analysis (LDA) was also used on the Au-CeO 2 results and showed separation between analytes as well as trends in gas concentration. Results indicate that each of the films are is selective towards O 2 , H 2 , CO, and NO 2 in separate exposures. However, when the films were analyzed in a sensor array based experiment, ie simultaneous exposures to the target gases, PCA analysis of the combined response showed an even greater selective character towards the target gases. Combined with the observed stability over long exposure periods, each of these Au-metal oxide films shows good potential as an optical sensing element for harsh environmental conditions.

47 OTHER INSTRUMENTATION↗

Ternary alloy material prediction using genetic algorithm and cluster expansion

This thesis summarizes our study on the crystal structures prediction of Fe-V-Si system using genetic algorithm and cluster expansion. Our goal is to explore and look for new stable compounds. We started from the current ten known experimental phases, and calculated formation energies of those compounds using density functional theory (DFT) package, namely, VASP. The convex hull was generated based on the DFT calculations of the experimental known phases. Then we did random search on some metal rich (Fe and V) compositions and found that the lowest energy structures were body centered cube (bcc) underlying lattice, under which we did our computational systematic searches using genetic algorithm and cluster expansion. Among hundreds of the searched compositions, thirteen were selected and DFT formation energies were obtained by VASP. The stability checking of those thirteen compounds was done in reference to the experimental convex hull. We found that the composition, 24-8-16, i.e., Fe 3 VSi 2 is a new stable phase and it can be very inspiring to the future experiments.

36 MATERIALS SCIENCE↗

Volumetrically Absorbing Thermal Insulator (VATI) for High-temperature Receivers

This project seeks to exploit volumetric absorption of concentrated solar irradiation in a thin, high-temperature, thermally conductive medium. High efficiency thermal conversion is achieved by volumetric absorption of both incoming solar irradiation (short wavelength) and emitted irradiation (long wavelength), demonstrating a volumetrically absorbing thermally insulating (VATI) effect. The thermalized energy is conducted to the back wall, enclosing the working fluid (molten salt or supercritical CO 2 ). Reliance on conductive thermal transport requires a thermally conductive medium, in the absence of which large temperature gradients drive losses due to emission. The project’s outcomes are important to realize a cost-effective approach to reduce optical and thermal losses from CSP receivers at high temperatures (720°C). High-temperature stable and commercially available porous SiC structures (open-cell foams) were explored as a volumetrically absorbing and thermally insulating layer. To the best of our knowledge, the current state-of-the-art for industrially deployed coatings is Pyromark. However, Pyromark suffers degradation at 700+°C and diurnal temperature changes. This necessitates periodic recoating, and the downtime increases the overall levelized cost of energy (LCOE) production. On the other hand, contemporary research activities have generated significant advances in the development of selective emitter coatings, which present challenges with costs, scalability, and stability. The pursued approach alleviates these concerns by developing a receiver that utilizes the inherent structure of high-temperature stable porous materials to enable robust and cost-effective receivers which require no periodic maintenance downtimes. The overall goal of the project is to experimentally demonstrate a figure of merit (FOM) of 0.92 at a temperature of 720°C and solar irradiation of 1000x concentration with porous receivers. The relevant crystallographic (phase) optical and thermal properties of porous SiC were first characterized. Second, the 3-D geometry of the porous SiC was analyzed using micro-X-ray tomography and converted to CAD data using image processing analysis. Utilizing this 3-D geometry and relevant optical/thermal properties, Monte Carlo- Ray Tracing (MCRT) analysis was performed to extract important parameters governing solar-thermal energy conversion such as extinction coefficient (β, 1/m), scattering albedo (ω) and the scattering phase function (Φ). These properties were then integrated into an in-house radiative and conduction transport model to solve for temperature and transport fluxes characterizing the solar-thermal energy conversion. This model was utilized to predict the FOM for various SiC porous geometries and to identify the highest possible FOM. Testing of the optimized porous structures will be accomplished with a custom-built high-accuracy (< ±4%) FOM measurement test-stand and a 1000x solar concentrator. When neglecting convective losses and resistance at the open boundary and the back wall, the optimized SiC foam leads to a FOM of 0.84. This FOM does not surpass the performance of Pyromark 2500. Yet, conversely to Pyromark 2500, SiC is stable at high temperatures and does not degrade over time. Also, it is possible to boost the FOM of SiC by engineering its effective thermal conductivity and its scattering albedo. A FOM of 0.92 is predicted for an optimized foam by accounting for convective losses and resistance at the open boundary and the back wall. This largely exceeds the FOM of Pyromark 2500 (~0.86) predicted by neglecting convective losses and resistance. Therefore, further engineering of the foam could lead to unprecedented FOMs.

14 SOLAR ENERGY↗

Space radiation resistant transparent polymeric materials

A literature search in the field of ultraviolet and charged particle irradiation of polymers was utilized in an experimental program aimed at the development of radiation stable materials for space applications. The rationale utilized for material selection and the synthesis, characterization and testing performed on several selected materials is described. Among the materials tested for ultraviolet stability in vacuum were: polyethyleneoxide, polyvinylnaphthalene, and the amino resin synthesized by the condensation of o-hydroxybenzoguanamine with formaldehyde. Particularly interesting was the radiation behavior of poly(ethyleneoxide), irradiation did not cause degradation of optical properties but rather an improvement in transparency as indicated by a decrease in solar absorptance with increasing exposure time.

Giori, C.↗

A low cost maritime control aircraft-ship-weapons system

It is pointed out that the long-range antiship standoff missile is emerging as the foremost threat on the seas. Delivered by high speed bombers, surface ships, and submarines, a missile attack can be mounted against selected targets from any point on the compass. An investigation is conducted regarding the configuration of a system which could most efficiently identify and destroy standoff threats before they launch their weapons. It is found that by using ships for carrying and launching missiles, and employing aircraft with a powerful radar only for search and missile directing operations, aircraft cost and weight can be greatly reduced. The employment of V/STOL aircraft in preference to other types of aircraft makes it possible to use ships of smaller size for carrying the aircraft. However, in order to obtain an all-weather operational capability for the system, ships are selected which are still big enough to display the required stability in heavy seas.

Fluk, H.↗