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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 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Micro-structural optimization of polybenzimidazole-based membranes for H2/CO2 separation at elevated temperatures

There is compelling need to develop novel separation methods to improve the energy efficiency of synthesis (syn) gas processing operations including H{sub 2} and H{sub 2}/CO production to meet power, chemicals, and fuel producer needs, as well as carbon capture and removal of other undesirable syngas impurities. To be technically and economically viable, a successful separation method must be applicable to industrially relevant gas streams at realistic process conditions and compatible with large gas volumes. H{sub 2} selective membrane technology is a promising method for syngas separations at elevated temperatures (>150 C) that could be positioned upstream or downstream of one or more of the water-gas-shift reactors (WGSRs) or integrated with a WGSR depending on application specific syngas processing. Polybenzimidazole (PBI)-based polymer chemistries are exceptional candidates for H{sub 2}/CO{sub 2} separations at elevated temperatures. In general, these materials possess excellent chemical resistance, very high glass transition temperatures (> 400 C), good mechanical properties, and an appropriate level of processability. Although commercially available PBI polymers have demonstrated commercially attractive H{sub 2}/CO{sub 2} selectivity, their H{sub 2} permeability is low. Our team s employing structural and chemical manipulations to tailor the polymer free-volume achitecture with the ultimate goal of enhancing H{sub 2} permselectivity while retaining the inherent hermochemical stability characteristics of PBI. We will discuss our synthetic approaches and their influences on the gas transport behavior of these PBI-based materials. In general, a decrease in H{sub 2}/CO{sub 2} selectivity was observed with an increase in H{sub 2} permeability. H{sub 2} permeability and H{sub 2}/CO{sub 2} selectivity at 250 C ranged from 50 to 1000 barrer and 5 to 45, respectively.

08 HYDROGEN↗
DOE OSTI2024

Ru/MgO catalyst with dual Ru structure sites for efficient CO production from CO 2 hydrogenation

The development and comprehension of supported metal catalysts for CO 2 hydrogenation is of paramount importance in mitigating the net CO 2 emissions. Supported Ru catalysts have been widely recognized in facilitating CO 2 methanation, on which recent findings suggest that the CO 2 hydrogenation process can be manipulated to favor the reverse water–gas shift (RWGS) pathway by precisely adjusting the size of Ru particles. However, the size-dependent impact of Ru remains a topic of lively debate. In this work, Ru/MgO catalysts with Ru in the form of single atoms (Ru 1 ) and few-atom cluster (Ru FAC ) structures were prepared for CO 2 hydrogenation. The 1.0Ru/MgO catalyst (with 1 wt.% of Ru), featuring a mixture of Ru 1 and Ru FAC with a size of 0.6–1.0 nm, showed the highest CO yield (38% at 500 °C) with balanced CO 2 conversion and CO selectivity. Transient CO 2 hydrogenation and temperature-programmed surface reaction (TPSR) studies suggested that the adsorbed CO 2 species participated in CO 2 hydrogenation. On Ru 1 sites, CO 2 hydrogenation followed the RWGS pathway, resulting in the production of CO. In contrast, on Ru FAC sites, the enhanced H 2 dissociation ability, along with the presence of adsorbed bidentate and monodentate carbonate species at the Ru-MgO interfaces, facilitated the formation of CH 4 through the CO 2 methanation pathway. In conclusion, this study highlights the critical roles of Ru structure and local environment in defining the CO 2 hydrogenation pathways and provides new design principles for highly active Ru-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The surface chemistry of cerium oxide

Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO 2 to CeO 2-X . The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

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

Multidisciplinary concurrent optimization framework for multi-phase building design process

Modern day building design projects require multidisciplinary expertise from architects and engineers across various phases of the design (conceptual, preliminary, and detailed) and construction processes. The Architecture Engineering and Construction (AEC) community has recently shifted gears toward leveraging design optimization techniques to make well-informed decisions in the design of buildings. However, most of the building design optimization efforts are either multidisciplinary optimization confined to just a specific design phase (conceptual/preliminary/detailed) or single disciplinary optimization (structural/thermal/daylighting/energy) spanning across multiple phases. Complexity in changing the optimization setup as the design progresses through subsequent phases, interoperability issues between modeling and physics-based analysis tools used at later stages, and the lack of an appropriate level of design detail to get meaningful results from these sophisticated analysis tools are few challenges that limit multi-phase multidisciplinary design optimization (MDO) in the AEC field. Here this paper proposes a computational building design platform leveraging concurrent engineering techniques such as interactive problem structuring, simulation-based optimization using meta models for energy and daylighting (machine learning based) and tradespace visualization. The proposed multi-phase concurrent MDO framework is demonstrated by using it to design and optimize a sample office building for energy and daylighting objectives across multiple phases. Furthermore, limitations of the proposed framework and future avenues of research are listed.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Electrocatalytic Hydrogenation of Biomass-Derived Organics: A review

Sustainable energy generation calls for a shift away from centralized, high-temperature, energy-intensive processes to decentralized, low-temperature conversions that can be powered by electricity produced from renewable sources. Electrocatalytic conversion of biomass-derived feedstocks would allow carbon recycling of distributed, energy-poor resources in the absence of sinks and sources of high-grade heat. Selective, efficient electrocatalysts that operate at low temperatures are needed for electrocatalytic hydrogenation (ECH) to upgrade the feedstocks. For effective generation of energy-dense chemicals and fuels, two design criteria must be met: (i) a high H:C ratio via ECH to allow for high-quality fuels and blends, and (ii) a lower O:C ratio in the target molecules via electrochemical decarboxylation/deoxygenation to improve the stability of fuels and chemicals. The goal of this review is to determine whether the following questions have been sufficiently answered in open literature, and if not, what additional information is required: (1) What organic functionalities are accessible for electrocatalytic hydrogenation under a set of reaction conditions? How do substitutions and functionalities impact the activity and selectivity of ECH? (2) What material properties cause an electrocatalyst to be active for ECH? Can general trends in ECH be formulated based on the type of electrocatalyst? (3) What is the impact of reaction (electrolyte concentration, pH, operating potential) and reactor type conditions?

Catalysts, redox reactions, hydrocarbons, Aromatic↗
DOE OSTI2026

Spatial Mapping of Valence Excited-State Landscapes Using Time-Resolved Shake-Down Spectroscopy

Time-resolved X-ray photoelectron spectroscopy (XPS) is used to track the photodissociation dynamics of 2-iodothiophene following 262 nm excitation. The transient XPS features include both direct ionization of the initially populated excited states and pronounced satellite peaks arising from shake-down processes. While the direct ionization signals exhibit only minimal energy shifts during C−I bond cleavage, the shake-down transitions undergo a substantial, 5 eV, shift over the reaction coordinate. By correlating these shifts with simulated C−I bond lengths, a direct structural mapping is established that reveals the exceptional sensitivity of shake-down channels to molecular geometry. These results demonstrate that shake-down transitions provide a new and powerful probe of ultrafast structural dynamics.

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

CO 2 Hydrogenation to Methanol over Inverse ZrO 2 /Cu(111) Catalysts: The Fate of Methoxy under Dry and Wet Conditions

Understanding the surface chemistry of CH 3 O species is essential for the production of methanol by CO 2 hydrogenation over Cu-based heterogeneous catalysts, as it facilitates the rational design of more efficient conversion processes. Recent research has identified inverse ZrO 2 /Cu catalysts as highly active and selective systems for the transformation of CO 2 to methanol with a performance that can be better than that of commercial Cu/ZnO catalysts. Here, we employed synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and calculations based on density functional theory (DFT) to understand the fate of CH 3 O groups under dry and wet environments. AP-XPS spectra revealed that under CO 2 hydrogenation conditions, formate and methoxy are two key intermediates to produce methanol. Furthermore, there are three different types of reactive sites on the surface: One is active for methoxy adsorption, which is stable and responsible for the methanol synthesis; Another one transforms CO 2 into CO; and a third one is active for CO 2 and methoxy dissociation, leading to C and methane formation. The theoretical calculations indicate that CH 3 OH readily dissociates to CH 3 O species following a highly exothermic (ΔE = -20.99 kcal/mol) and barrierless process. The water produced by the reverse water-gas shift reaction (CO 2 + H 2 → H 2 O + CO) can prevent the decomposition of CH 3 O species. We discovered that by introducing a tiny amount of water vapor (2 × 10 -6 Torr) into the reaction chamber, the energy barrier for the reaction CH 3 O(ads) + H(ads) → CH 3 OH(gas) is dramatically reduced. AP-XPS and computational modelling showed that water is quite capable of extracting adsorbed methoxy to form gaseous methanol. With this in mind, one could boost the methanol selectivity by adding appropriate amounts of water or steam, which is an inexpensive and feasible solution for industrial operations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanically Accelerated Depolymerization of Entangled Linear Polymer Melts

Mechanical forces can enhance the chemical depolymerization of synthetic polymers when shear flow accelerates chain scission. To quantify the extent of mechanically-accelerated scission, the effect of simple shear flow (duration and strength) with low Weissenberg and Deborah numbers was investigated by considering the impact of applied work in both simple shear and shear dominated mixed flows. Hydrogenated polyisoprene was chosen as a model linear, entangled system. The conditions (strain amplitude, frequency, and shearing time) necessary to increase chain scission were assessed in the rubbery melt. Shear flow accelerated chain scission at higher temperatures, suggesting an activated process. Isothermal scission versus work curves were superposed by applying shift factors a T,S , whose Arrhenius-like temperature dependence gave an apparent activation energy for chain scission of ~ 110 kJ/mol, which is likely a combination of the activation energy of viscosity and bond energy. This work provides a base for quantifying the impact of shear on depolymerization of polymer melts and highlight the connection between viscous dissipation and scission chemistry.

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

High-Quality Surface Plasmon Polaritons in Large-Area Sodium Nanostructures

Sodium (Na) is predicted to be an ideal plasmonic material with ultralow optical loss across visible to near-infrared (NIR). However, there has been limited research on Na plasmonics. We develop a scalable fabrication method for Na nanostructures by combining phase-shift photolithography and a thermo-assisted spin-coating process. Using this method, we fabricated Na nanopit arrays with varying periodicities (300-600 nm) and with tunable surface plasmon polariton (SPP) modes spanning visible to NIR. We achieved SPP resonances as narrow as 9.3 nm. In addition, Na nanostructures showed line width narrowing from visible toward NIR, showing their prospect operating in the NIR. To address the challenges associated with the high reactivity of Na, we designed a simple encapsulation strategy and stabilized the Na nanostructures in ambient conditions for more than two months. As a low-cost and low-loss plasmonic material, Na offers a competitive option for nanophotonic devices and plasmon-enhanced applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Quantifying Disconnection of Groundwater From Managed‐Ephemeral Surface Water During Drought and Conjunctive Agricultural Use

Abstract The physics of disconnection between interrelated surface and groundwater has evolved considerably in recent years, especially since conjunctive use of water resources is increasingly dependent on groundwater resilience, but methods to measure disconnection on a river basin scale are lacking especially for managed‐ephemeral and irrigated‐agricultural systems. Multiyear drought limited surface water along Rincon Valley within the Elephant Butte Irrigation District (EBID) in the arid, Lower Rio Grande Basin of south‐central New Mexico, USA, and effects were compounded by continued extraction of groundwater to meet crop requirements. Average year‐end water table elevations in recent years have been below the average elevation of the riverbed, indicating potential disconnection between the river and the aquifer even when the river flows during the irrigation season. This study analyzed data from EBID groundwater monitoring wells adjacent to the river, infiltration determined from river flows, and riverbed measurements along the Rincon Valley reach to determine net annual seepage discharge to the aquifer and annual average pressure head below the river. Annual assessment from 2010 to 2017 confirmed that the drought shifted the system from connection to transition and then to disconnection. Nonlinear regression was used to quantify this shift to disconnection and back, enabled determination of several disconnection process metrics, and was also used to confirm that nonlinear disconnection behavior was reversible without significant hysteresis. The method developed herein confirms that the total head difference transition threshold can be determined from river/riparian monitoring sites over reach to basin scales.

Fuchs, Erek H.↗
DOE OSTI2022

Dynamic compression of Ce and Pr with millisecond time-resolved X-ray diffraction

Abstract Both cerium (Ce) and praseodymium (Pr) undergo a volume collapse transition under compression that originate from similar electronic mechanisms. Yet the outcome could not be more different. In the case of Ce with one affected 4f electron the volume collapse leaves the crystal symmetry intact, whereas for Pr with two 4f electrons the crystal symmetry changes from a distorted face centered cubic structure to a lower symmetry orthorhombic structure. In this paper, we present a study of the effect of strain/compression rate spanning nearly 4 orders of magnitude on the volume collapse phase transitions in Ce and Pr. These dynamic compression experiments in a diamond anvil cell also reveal kinetic differences between the phase transformations observed in these two materials. The transition cannot be overdriven in pressure in Ce, which indicates a fast kinetic process, whereas fast compression rates in Pr lead to a shift of the phase boundary to higher pressures, pointing to slower kinetics possibly due to the realization of a new crystal structure.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Fast ion charge exchange spectroscopy adapted for tangential viewing geometry in LHD

A tangential Fast Ion Charge eXchange Spectroscopy is newly applied on a Large Helical Device (LHD) for co/countercirculating fast ions, which are produced by high energy tangential negative-ion based neutral beam injection. With this new observation geometry, both the tangential-neutral beam (NB) and a low-energy radial-NB based on positive ions can be utilized as probe beams of the measurement. We have successfully observed Doppler-shifted H-alpha lights due to the charge exchange process between the probing NB and circulating hydrogen ions of around 100 keV in LHD plasmas.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2014

Effect of Er doping on the structural and magnetic properties of cobalt-ferrite

Nanocrystalline particulates of Er doped cobalt-ferrites CoFe{sub (2−x)}Er{sub x}O{sub 4} (0 ≤ x ≤ 0.04), were synthesized, using sol-gel assisted autocombustion method. Co-, Fe-, and Er- nitrates were the oxidizers, and malic acid served as a fuel and chelating agent. Calcination (400–600 °C for 4 h) of the precursor powders was followed by sintering (1000 °C for 4 h) and structural and magnetic characterization. X-ray diffraction confirmed the formation of single phase of spinel for the compositions x = 0, 0.01, and 0.02; and for higher compositions an additional orthoferrite phase formed along with the spinel phase. Lattice parameter of the doped cobalt-ferrites was higher than that of pure cobalt-ferrite. The observed red shift in the doped cobalt-ferrites indicates the presence of induced strain in the cobalt-ferrite matrix due to large size of the Er{sup +3} compared to Fe{sup +3}. Greater than two-fold increase in coercivity (∼66 kA/m for x = 0.02) was observed in doped cobalt-ferrites compared to CoFe{sub 2}O{sub 4} (∼29 kA/m)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Direct experimental determination of spectral densities of molecular complexes

Determining the spectral density of a molecular system immersed in a proteomic scaffold and in contact to a solvent is a fundamental challenge in the coarse-grained description of, e.g., electron and energy transfer dynamics. Once the spectral density is characterized, all the time scales are captured and no artificial separation between fast and slow processes need to be invoked. Based on the fluorescence Stokes shift function, we utilize a simple and robust strategy to extract the spectral density of a number of molecular complexes from available experimental data. Specifically, we show that experimental data for dye molecules in several solvents, amino acid proteins in water, and some photochemical systems (e.g., rhodopsin and green fluorescence proteins), are well described by a three-parameter family of sub-Ohmic spectral densities that are characterized by a fast initial Gaussian-like decay followed by a slow algebraic-like decay rate at long times.

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

Ion emission from warm dense matter produced by irradiation with a soft x-ray free-electron laser

Here we report on an experiment performed at the FLASH2 free-electron laser (FEL) aimed at producing warm dense matter via soft x-ray isochoric heating. In the experiment, we focus on study of the ions emitted during the soft x-ray ablation process using time-of-flight electron multipliers and a shifted Maxwell–Boltzmann velocity distribution model. We find that most emitted ions are thermal, but that some impurities chemisorbed on the target surface, such as protons, are accelerated by the electrostatic field created in the plasma by escaped electrons. The morphology of the complex crater structure indicates the presence of several ion groups with varying temperatures. We find that the ion sound velocity is controlled by the ion temperature and show how the ion yield depends on the FEL radiation attenuation length in different materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2012

THE BOSS EMISSION-LINE LENS SURVEY (BELLS). I. A LARGE SPECTROSCOPICALLY SELECTED SAMPLE OF LENS GALAXIES AT REDSHIFT {approx}0.5

We present a catalog of 25 definite and 11 probable strong galaxy-galaxy gravitational lens systems with lens redshifts 0.4 {approx}< z {approx}< 0.7, discovered spectroscopically by the presence of higher-redshift emission lines within the Baryon Oscillation Spectroscopic Survey (BOSS) of luminous galaxies, and confirmed with high-resolution Hubble Space Telescope (HST) images of 44 candidates. Our survey extends the methodology of the Sloan Lens Advanced Camera for Surveys survey (SLACS) to higher redshift. We describe the details of the BOSS spectroscopic candidate detections, our HST ACS image processing and analysis methods, and our strong gravitational lens modeling procedure. We report BOSS spectroscopic parameters and ACS photometric parameters for all candidates, and mass-distribution parameters for the best-fit singular isothermal ellipsoid models of definite lenses. Our sample to date was selected using only the first six months of BOSS survey-quality spectroscopic data. The full five-year BOSS database should produce a sample of several hundred strong galaxy-galaxy lenses and in combination with SLACS lenses at lower redshift, strongly constrain the redshift evolution of the structure of elliptical, bulge-dominated galaxies as a function of luminosity, stellar mass, and rest-frame color, thereby providing a powerful test for competing theories of galaxy formation and evolution.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

A LINK TO THE PAST: USING MARKOV CHAIN MONTE CARLO FITTING TO CONSTRAIN FUNDAMENTAL PARAMETERS OF HIGH-REDSHIFT GALAXIES

We have developed a new method for fitting spectral energy distributions (SEDs) to identify and constrain the physical properties of high-redshift (4 < z < 8) galaxies. Our approach uses an implementation of Bayesian based Markov Chain Monte Carlo that we have dubbed '{pi}MC{sup 2}'. It allows us to compare observations to arbitrarily complex models and to compute 95% credible intervals that provide robust constraints for the model parameters. The work is presented in two sections. In the first, we test {pi}MC{sup 2} using simulated SEDs to not only confirm the recovery of the known inputs but to assess the limitations of the method and identify potential hazards of SED fitting when applied specifically to high-redshift (z > 4) galaxies. In the second part of the paper we apply {pi}MC{sup 2} to thirty-three 4 < z < 8 objects, including the spectroscopically confirmed Grism ACS Program for Extragalactic Science Ly{alpha} sample (4 < z < 6), supplemented by newly obtained Hubble Space Telescope/WFC3 near-IR observations, and several recently reported broadband selected z > 6 galaxies. Using {pi}MC{sup 2}, we are able to constrain the stellar mass of these objects and in some cases their stellar age and find no evidence that any of these sources formed at a redshift larger than z = 8, a time when the universe was Almost-Equal-To 0.6 Gyr old.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

DWARF GALAXY FORMATION WITH H{sub 2}-REGULATED STAR FORMATION. II. GAS-RICH DARK GALAXIES AT REDSHIFT 2.5

We present a cosmological hydrodynamic simulation of the formation of dwarf galaxies at redshifts z ∼> 2.5 using a physically motivated model for H{sub 2}-regulated star formation. Our simulation, performed using the Enzo code and reaching a peak resolution of 109 proper parsecs at z = 2.5, extends the results of Kuhlen et al. to significantly lower redshifts. We show that a star formation prescription regulated by the local H{sub 2} abundance leads to the suppression of star formation in dwarf galaxy halos with M{sub h} ∼< 10{sup 10} M{sub ☉} and to a large population of gas-rich 'dark galaxies' at z = 2.5 with low star formation efficiencies and gas depletion timescales >20 Gyr. The fraction of dark galaxies is 60% at M{sub h} ≅ 10{sup 10} M{sub ☉} and increases rapidly with decreasing halo mass. Dark galaxies form late and their gaseous disks never reach the surface densities, ∼> 5700 M{sub ☉} pc{sup –2} (Z/10{sup –3} Z{sub ☉}){sup –0.88}, that are required to build a substantial molecular fraction. Despite this large population of dark galaxies, we show that our H{sub 2}-regulated simulation is consistent with both the observed luminosity function of galaxies and the cosmological mass density of neutral gas at z ∼> 2.5. Moreover, our results provide a theoretical explanation for the recent detection in fluorescent Lyα emission of gaseous systems at high redshift with little or no associated star formation. We further propose that H{sub 2}-regulation may offer a fresh solution to a number of outstanding 'dwarf galaxy problems' in ΛCDM. In particular, H{sub 2}-regulation leads galaxy formation to become effectively stochastic on mass scales of M{sub h} ∼ 10{sup 10} M{sub ☉}, and thus these massive dwarfs are not 'too big to fail'.

79 ASTRONOMY AND ASTROPHYSICS↗