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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Engineering bimetallic interfaces and revealing the mechanism for carbon dioxide electroreduction to C 3+ liquid chemicals

Reduction reaction of CO 2 (CO 2 RR) to liquid C 3+ chemicals is a net-zero-carbon process and can increase local resiliency to power outages and fuel consumption. The mechanism and the catalyst design rules of CO 2 RR-to-C 3+ are unknown. Engineering bimetallic interface (e.g., Pd/Au) to tune the intermediate adsorption is promising for promoting C 3+ formation. Our density functional theory (DFT) calculations find that *CH 2 could be the key intermediate and C 1 -CH 2 coupling could be the rate-limiting step to generate C 3+ . High CO surface coverages can promote the bimetallic interfacial sites, lower the energetics of the C 1 -CH 2 coupling step, and enhance the C 3+ formation. We further construct a volcano plot of C 1 -CH 2 kinetics as a function of the binding strength of key intermediate *CH 2 via engineering the d-band center of the interfacial site. Our findings could guide the rational design of bimetallic interfaces and their near-surface microenvironment for enhancing CO 2 RR-to-C 3+ .

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2017

Yukawa sector of minimal SO(10) unification

Here, we show that in SO(10) models, a Yukawa sector consisting of a real 10H, a real 120 H and a complex 126 H of Higgs fields can provide a realistic fit to all fermion masses and mixings, including the neutrino sector. Although the group theory of SO(10) demands that the 10 H and 120 H be real, most constructions complexify these fields and impose symmetries exterior to SO(10) to achieve predictivity. The proposed new framework with real 10H and real 120 H relies only on SO(10) gauge symmetry, and yet has a limited number of Yukawa parameters. Our analysis shows that while there are restrictions on the observables, a good fit to the entire fermion spectrum can be realized. Unification of gauge couplings is achieved with an intermediate scale Pati-Salam gauge symmetry. Proton decay branching ratios are calculable, with the leading decay modes being p→ $\bar{v}$π + and p→ e + π 0 .

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction

Formic acid (or formate) is suggested to be one of the most economically viable products from electrochemical carbon dioxide reduction. However, its commercial viability hinges on the development of highly active and selective electrocatalysts. Here we report that structural defects have a profound positive impact on the electrocatalytic performance of bismuth. Bismuth oxide double-walled nanotubes with fragmented surface are prepared as a template, and are cathodically converted to defective bismuth nanotubes. This converted electrocatalyst enables carbon dioxide reduction to formate with excellent activity, selectivity and stability. Most significantly, its current density reaches ~288 mA cm -2 at -0.61 V versus reversible hydrogen electrode within a flow cell reactor under ambient conditions. Using density functional theory calculations, the excellent activity and selectivity are rationalized as the outcome of abundant defective bismuth sites that stabilize the *OCHO intermediate. Furthermore, this electrocatalyst is coupled with silicon photocathodes and achieves high-performance photoelectrochemical carbon dioxide reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

A design for a compact time-of-flight mass spectrometer

The design of a prototype, compact time-of-flight (TOF) mass spectrometer (MS) is described. The system primarily consists of an ion acceleration/focusing/steering assembly (AFSA), an 8 cm field-free region, a 4 cm, dual-stage reflectron and a miniature microchannel plate detector. Consequently, the resulting flight length of the system is 12 cm. The system has been designed with the capability to sample directly from atmosphere at ambient pressures. This is accomplished through the use of an electrodynamic ion funnel, housed in an intermediate-vacuum chamber that is coupled to the inlet of the TOF chamber. TOF spectra were obtained using noble gases (Ar, Kr and Xe) as test chemicals. These measured flight times were used to probe the performance of the instrument. A temporal resolution (tflight/Δt) of approximately 125, acquired using 129Xe+, has been measured for the system.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2012

TWO-COMPONENT STRUCTURE OF THE H{beta} BROAD-LINE REGION IN QUASARS. I. EVIDENCE FROM SPECTRAL PRINCIPAL COMPONENT ANALYSIS

We report on a spectral principal component analysis (SPCA) of a sample of 816 quasars, selected to have small Fe II velocity shifts with spectral coverage in the rest wavelength range 3500-5500 A. The sample is explicitly designed to mitigate spurious effects on SPCA induced by Fe II velocity shifts. We improve the algorithm of SPCA in the literature and introduce a new quantity, the fractional-contribution spectrum, that effectively identifies the emission features encoded in each eigenspectrum. The first eigenspectrum clearly records the power-law continuum and very broad Balmer emission lines. Narrow emission lines dominate the second eigenspectrum. The third eigenspectrum represents the Fe II emission and a component of the Balmer lines with kinematically similar intermediate-velocity widths. Correlations between the weights of the eigenspectra and parametric measurements of line strength and continuum slope confirm the above interpretation for the eigenspectra. Monte Carlo simulations demonstrate the validity of our method to recognize cross talk in SPCA and firmly rule out a single-component model for broad H{beta}. We also present the results of SPCA for four other samples that contain quasars in bins of larger Fe II velocity shift; similar eigenspectra are obtained. We propose that the H{beta}-emitting region has two kinematically distinct components: one with very large velocities whose strength correlates with the continuum shape and another with more modest, intermediate velocities that is closely coupled to the gas that gives rise to Fe II emission.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Piezoelectric polar nanoregions and relaxation-coupled resonances in relaxor ferroelectrics

It is a generally accepted fact that the unique dielectric properties of relaxor ferroelectrics are related to the formation of polar nanoregion (PNRs). Less well recognized is the corollary that, because they are polar and therefore lack inversion symmetry, PNRs are also piezoelectric at the nanoscale and can therefore behave as nanoresonators. Using the particular relaxor ferroelectric K 1–x Li x TaO 3 (KLT), we show that, when electrically excited into oscillation, these piezoelectric nanoresonators can drive macroscopic electromechanical resonances. Unexpectedly, however, pairs of coupled resonances corresponding to a particular type of oscillation are observed, with one of the resonance exhibiting a characteristic Fano-like line shape. The complex resonance spectra can be described equally well by two alternative but complementary models both involving two resonances coupled through a relaxation: a purely classical one based on two coupled damped harmonic oscillators and a semiclassical based on two discrete excitations coupled to each other through a continuum. Together, they provide complementary perspectives on the underlying physics of the system. Both reproduce the rapid evolution of the resonance spectrum across three wide temperature ranges, including a phase transition range. In the high-temperature range, the coupling between modes is due to the collective π relaxation of the lithium ions within PNRs and, in the phase transition range, to “heterophase relaxation” of the surrounding lattice between its high-temperature cubic and low-temperature tetragonal phases, both coherent effects. Here, the coupling is suppressed in the intermediate range of the collective π/2 relaxation of the lithium ions. Incidentally, the measured dielectric spectra are shown to bear a surprising but justifiable resemblance to the optical spectra of certain atomic vapors exhibiting electromagnetically induced transparency.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Topological Transitions Induced by Antiferromagnetism in a Thin-Film Topological Insulator

Magnetism in topological insulators (TIs) opens a topologically nontrivial exchange band gap, providing an exciting platform for manipulating the topological order through an external magnetic field. Here, we show that the surface of an antiferromagnetic thin film can magnetize the top and the bottom TI surface states through interfacial couplings. During the magnetization reversal, intermediate spin configurations are ascribed from unsynchronized magnetic switchings. This unsynchronized switching develops antisymmetric magnetoresistance spikes during magnetization reversals, which might originate from a series of topological transitions. With the high Néel ordering temperature provided by the antiferromagnetic layers, the signature of the induced topological transition persists up to ~$90 K$.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Integrating CO2 Electrolysis with Gas Fermentation to Produce Valuable Fuels and Chemicals

Many industrial activities squander CO2, decreasing process yield. We envision a future where this waste carbon is instead captured, upgraded, and valorized directly at the point of emission. Within the CO2 Reduction and Upgrading Consortium (a collaboration of seven US national laboratories and industrial partners), we are pursuing this goal by developing and de-risking new technologies for low temperature CO2 electrolysis, coupled with biological upgrading of intermediates into more valuable compounds. One such process involves electrocatalytic reduction of CO2 to generate carbon monoxide (CO). As both a carbon and energy source, CO represents an attractive feedstock for microbial upgrading by certain syngas-fermenting species, such as the autotrophic bacterium Clostridium autoethanogenum. Our team has developed new genetic tools and optimized cultivation techniques to enhance C. autoethanogenum as a platform host for the biological conversion of syngas into value-added products. For example, we have created novel CRISPR-based genetic engineering techniques to build new, genome-reduced, platform strains of C. autoethanogenum with improved growth rates. Further, we ve introduced heterologous biochemical pathways into C. autoethanogenum to enable the production of high-value compounds from syngas, such as the isoprenoid precursor mevalonic acid. With the tools of electrochemistry and synthetic biology, there is virtually no limit to the spectrum of products that could be sustainably manufactured from CO2.

09 BIOMASS FUELS↗
NASA NTRS1991

Design considerations for space radiators based on the liquid sheet (LSR) concept

Concept development work on space heat rejection subsystems tailored to the requirements of various space power conversion systems is proceeding over a broad front of technologies at NASA LeRC. Included are orbital and planetary surface based radiator concepts utilizing pumped loops, a variety of heat pipe radiator concepts, and the innovative liquid sheet radiator (LSR). The basic feasibility of the LSR concept was investigated in prior work which generated preliminary information indicating the suitability of the LSR concept for space power systems requiring cycle reject heat to be radiated to the space sink at low-to-mid temperatures (300 to 400 K), with silicon oils used for the radiator working fluid. This study is directed at performing a comparative examination of LSR characteristics as they affect the basic design of low earth orbit solar dynamic power conversion systems. The power systems considered were based on the closed Brayton (CBC) and the Free Piston Stirling (FPS) cycles, each with a power output of 2 kWe and using previously tested silicone oil (Dow-Corning Me2) as the radiator working fluid. Conclusions indicate that, due to its ability for direct cold end cooling, an LSR based heat rejection subsystem is far more compatible with a Stirling space power system than with a CBC, which requires LSR coupling by means of an intermediate gas/liquid heat exchanger and adjustment of cycle operating conditions.

Juhasz, Albert J.↗
NASA NTRS1991

Design considerations for space radiators based on the liquid sheet (LSR) concept

This study is directed at performing a comparative examination of LSR characteristics as they affect the basic design of low earth orbit solar dynamic conversion systems. The power systems considered were based on the closed Brayton (CBC) and the free piston Stirling (FPS) cycles, each with a power output of 2 kWe and using previously tested silicone oil (Dow-Corning Me2) as the radiator working fluid. Conclusions indicate that, due to its ability for direct cold end cooling, an LSR based heat rejection subsystem is far more compatible with a Stirling space power system than with a CBC, which requires LSR coupling by means of an intermediate gas/liquid heat exchanger and adjustment of cycle operating conditions.

Juhasz, Albert J.↗
DOE OSTI2015

Microsystem enabled photovoltaic modules and systems

A microsystem enabled photovoltaic (MEPV) module including: an absorber layer; a fixed optic layer coupled to the absorber layer; a translatable optic layer; a translation stage coupled between the fixed and translatable optic layers; and a motion processor electrically coupled to the translation stage to controls motion of the translatable optic layer relative to the fixed optic layer. The absorber layer includes an array of photovoltaic (PV) elements. The fixed optic layer includes an array of quasi-collimating (QC) micro-optical elements designed and arranged to couple incident radiation from an intermediate image formed by the translatable optic layer into one of the PV elements such that it is quasi-collimated. The translatable optic layer includes an array of focusing micro-optical elements corresponding to the QC micro-optical element array. Each focusing micro-optical element is designed to produce a quasi-telecentric intermediate image from substantially collimated radiation incident within a predetermined field of view.

14 SOLAR ENERGY↗
DOE OSTI2023

In Situ Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes

In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.

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

Atomistic mechanisms for catalytic transformations of NO to NH3, N2O, and N2 by Pd

The industrial pollutant NO is a potential threat to the environment and to human health. Thus, selective catalytic reduction of NO into harmless N2, NH3, and/or N2O gas is of great interest. Among many catalysts, metal Pd has been demonstrated to be most efficient for selectivity of reducing NO to N2. However, the reduction mechanism of NO on Pd, especially the route of N−N bond formation, remains unclear, impeding the development of new, improved catalysts. We report here the elementary reaction steps in the reaction pathway of reducing NO to NH3, N2O, and N2, based on density functional theory (DFT)-based quantum mechanics calculations. We show that the formation of N2O proceeds through an Eley-Rideal (E−R) reaction pathway that couples one adsorbed NO* with one non−adsorbed NO from the solvent or gas phase. This reaction requires high NO* surface coverage, leading first to the formation of the trans-(NO)2* intermediate with a low N−N coupling barrier (0.58 eV). Notably, trans-(NO)2* will continue to react with NO in the solvent to form N2O, that has not been reported. With the consumption of NO and the formation of N2O* in the solvent, the Langmuir-Hinshelwood (L-H) mechanism will dominate at this time, and N2O* will be reduced by hydrogenation at a low chemical barrier (0.42 eV) to form N2. In contrast, NH3 is completely formed by the L-H reaction, which has a higher chemical barrier (0.87 eV). Our predicted E-R reaction has not previously been reported, but it explains some existing experimental observations. In addition, we examine how catalyst activity might be improved by doping a single metal atom (M) at the NO* adsorption site to form M/Pd and show its influence on the barrier for forming the N−N bond to provide control over the product distribution.

Physics↗
DOE OSTI2024

Divergent Bimetallic Mechanisms in Copper(II)-Mediated C–C, N–N, and O–O Oxidative Coupling Reactions

Copper-catalyzed aerobic oxidative coupling of diaryl imines provides a route for conversion of ammonia to hydrazine. Here the present study uses experimental and density functional theory computational methods to investigate the mechanism of N–N bond formation, and the data support a mechanism involving bimolecular coupling of Cu-coordinated iminyl radicals. Computational analysis is extended to Cu II -mediated C–C, N–N, and O–O coupling reactions involved in the formation of cyanogen (NC–CN) from HCN, 1,3-butadiyne from ethyne (i.e., Glaser coupling), hydrazine from ammonia, and hydrogen peroxide from water. The results reveal two different mechanistic pathways. Heteroatom ligands with an uncoordinated lone pair (iminyl, NH 2 , OH) undergo charge transfer to Cu II , generating ligand-centered radicals that undergo facile bimolecular radical–radical coupling. Ligands lacking a lone pair (CN and CCH) form bridged binuclear diamond-core structures that undergo C–C coupling. This mechanistic bifurcation is rationalized by analysis of spin densities in key intermediates and transition states, as well as multiconfigurational calculations. Radical–radical coupling is especially favorable for N–N coupling owing to energetically favorable charge transfer in the intermediate and thermodynamically favorable product formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1971

Adavanced RTG and thermoelectric materials study

A comprehensive, generalized two-dimensional RTG analysis computer program was developed. This program is capable of analyzing any specified RTG design under a wide range of transient as well as steady-state operating conditions. The feasibility of a new concept for the design of segmented (or single-phase) thermoelectric couples was demonstrated. A SiGe-PbTe segmented couple involving pressure contacted junctions at the intermediate- and hot-junction temperatures was successfully encapsulated in a hermetically sealed bellows enclosure. This bellows-encapsulated couple was operated between a hot- and cold-junction temperature of 1200 K and 450 K, respectively, with a measured energy conversion efficiency of 7.6 + or - .5 per cent. An experimental study of selected sublimation barrier schemes revealed that a significant reduction in the sublimation rate of p-type PbTe could be achieved by using multiple layers of SiO2 fibers. A comparison of the barrier effectiveness is given for three different barrier designs.

Eggers, P. E.↗