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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 1,693 records · Page 94
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Nitrogen-doped carbons derived from poly(ionic liquid)s with various backbones and cations

In this study, poly(ionic liquid)s (PILs) with various backbone/cation pairings (backbones - ethyl methacrylate, styrene; covalently attached cations - butylimidazolium, trimethylammonium, butylpyrrolidinium) were successfully synthesized as carbon precursors. Pyrolysis of PILs produced carbons with sheet-like structures with a metallic luster in contrast to the powder form of carbons produced from polyacrylonitrile. The results also show that cation type has a significant impact on surface area, graphitic content, graphitic nitrogen content, nitrogen retention, carbon yield and surface chemistry of the PIL-derived carbons. The design of nitrogen-doped carbons based on a diverse set of PILs with various cation and polymer backbone chemistries may be an effective strategy to optimize carbon properties for subsequent application in energy storage devices.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Evolution of silicon bulk lifetime during III–V‐on‐Si multijunction solar cell epitaxial growth

Abstract The evolution of Si bulk minority carrier lifetime during the heteroepitaxial growth of III–V on Si multijunction solar cell structures via metal‐organic chemical vapor deposition (MOCVD) has been analyzed. In particular, the impact on Si lifetime resulting from the four distinct phases within the overall MOCVD‐based III–V/Si growth process were studied: (1) the Si homoepitaxial emitter/cap layer; (2) GaP heteroepitaxial nucleation; (3) bulk GaP film growth; and (4) thick GaAs y P 1‐y compositionally graded metamorphic buffer growth. During Phase 1 (Si homoepitaxy), an approximately two order of magnitude reduction in the Si minority carrier lifetime was observed, from about 450 to ≤1 µs. However, following the GaP nucleation (Phase 2) and thicker film (Phase 3) growths, the lifetime was found to increase by about an order of magnitude. The thick GaAs y P 1‐y graded buffer was then found to provide further recovery back to around the initial starting value. The most likely general mechanism behind the observed lifetime evolution is as follows: lifetime degradation during Si homoepitaxy because of the formation of thermally induced defects within the Si bulk, with subsequent lifetime recovery due to passivation by fast‐diffusing atomic hydrogen coming from precursor pyrolysis, especially the group‐V hydrides (PH 3 , AsH 3 ), during the III–V growth. These results indicate that the MOCVD growth methodology used to create these target III–V/Si solar cell structures has a substantial and dynamic impact on the minority carrier lifetime within the Si substrate. Copyright © 2015 John Wiley & Sons, Ltd.

García‐Tabarés, Elisa↗
DOE OSTI2019

Single Fe Atom on Hierarchically Porous S, N-Codoped Nanocarbon Derived from Porphyra Enable Boosted Oxygen Catalysis for Rechargeable Zn-Air Batteries

Iron-nitrogen-carbon materials (Fe-N-C) are known for their excellent oxygen reduction reaction (ORR) performance. Unfortunately, they generally show a laggard oxygen evolution reaction (OER) activity, which results in a lethargic charging performance in rechargeable Zn-air batteries. Here porous S-doped Fe-N-C nanosheets are innovatively synthesized utilizing a scalable FeCl 3 -encapsulated-porphyra precursor pyrolysis strategy. The obtained electrocatalyst exhibits ultrahigh ORR activity ( E 1/2 = 0.84 V vs reversible hydrogen electrode) and impressive OER performance ( E j=10 = 1.64 V). The potential gap (Δ E = E j=10 - E 1/2 ) is 0.80 V, outperforming that of most highly active bifunctional electrocatalysts reported to date. Furthermore, the key role of S involved in the atomically dispersed Fe-N x species on the enhanced ORR and OER activities is expounded for the first time by ultrasound-assisted extraction of the exclusive S source (taurine) from porphyra. Moreover, the assembled rechargeable Zn-air battery comprising this bifunctional electrocatalyst exhibits higher power density (225.1 mW cm -2 ) and lower charging-discharging overpotential (1.00 V, 100 mA cm -2 compared to Pt/C + RuO 2 catalyst). Here, the design strategy can expand the utilization of earth-abundant biomaterial-derived catalysts, and the mechanism investigations of S doping on the structure-activity relationship can inspire the progress of other functional electrocatalysts.

25 ENERGY STORAGE↗
DOE OSTI2021

Nanoarchitectonics of Metal–Organic Frameworks for Capacitive Deionization via Controlled Pyrolyzed Approaches

Abstract Next‐generation desalination technologies are needed to meet the increasing demand for clean water. Capacitive deionization (CDI) is a thermodynamically efficient technique to treat non‐potable water with relatively low salinity. The salt removal capacity and rate of CDI are highly dependent on the electrode materials, which are preferentially porous to store ions through electrosorption and/or redox reactions. Metal–organic frameworks (MOFs) with “infinite” combinations of transition metals and organic linkers simplify the production of carbonaceous materials often with redox‐active components after pyrolysis. MOFs‐derived materials show great tunability in both compositions and structures but require further refinement to improve CDI performance. This review article summarizes recent progress in derivatives of MOFs and MOF‐like materials used as CDI electrodes, focusing on the structural and compositional material considerations as well as the processing parameters and electrode architectures of the device. Furthermore, the challenges and opportunities associated with this research area are also discussed.

Wang, Hao↗
DOE OSTI2023

Impact of biochar amendments on soil water and plant uptake dynamics under different cropping systems

Abstract Application of biochar amendments in agricultural systems has received much attention in recent years. In this study, we assess the 5‐year impacts of biochar application on soil water and plant interactions for an irrigated fresh market tomato ( Solanum lycopersicum ) and a rainfed pasture ( Poaceae ) cropping system. In particular, we focus on three varieties of locally produced biochar from agricultural waste materials—almond shell, walnut shell, and almond pruning residues that are pyrolyzed using a mobile pyrolysis unit. We used the soil hydrological model HYDRUS‐1D to explicitly track seasonal and annual soil water fluxes through changes in water retention, drainage, evaporation, and plant water uptake under biochar application. Modeling results show that the application of biochar at 5% increased soil water availability within the top 20 cm for a rainfed system, irrespective of biochar amendment type. This is clearly indicative of higher plant water uptake and greater water use efficiency (WUE) under biochar application. In contrast, a similar biochar amendment for the irrigated system did not affect WUE, instead reducing seasonal soil evaporation loss and thereby reducing irrigation demand. In both cropping systems, year‐to‐year variability in precipitation significantly impacted the total amount of water saved under biochar application with certain amendments retaining more water than others. Given that biochar application increased water retention irrespective of cropping systems, we further used a simple approach to determine yield trade‐off, if any, between control and biochar treatments. Our economic balance clearly demonstrates that the water saved by amending soil with biochar does not offset the yield disparity if compensated with carbon credits and therefore, application of biochar should be actively considered for both its direct and indirect benefits to potential greenhouse gas mitigation (e.g., diverting orchard waste from open burning), water savings, and soil health.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

The role of stereochemistry in combustion processes

Stereochemical effects significantly influence chemical processes, yet it is not well understood if they are a leading source of uncertainty in combustion modeling. Stereochemistry influences a combustion model (i) at the earliest stage of its construction when mapping the reaction network, (ii) in the computation of individual thermochemical and rate parameters, and (iii) in the prediction of combustion observables. The present work reviews the importance of enumerating stereochemical species and reactions at each of these steps. Further, it analyzes the separate influence of several types of stereochemistry, including geometric, optical, and fleeting transition state diastereomers. Three reaction networks serve to examine which stages of low-temperature oxidation are most affected by stereochemistry, including the first and second oxidation of n-butane, the third oxidation of n-pentane, and the early stages of pyrolysis of 1- and 2-pentene. The 149 reactions in the n-butane mechanism are expanded to 183 reactions when accounting for diastereomerism. Each of these 183 reactions is parameterized with ab initio kinetics computations to determine that, for the n-butane mechanism, the median factor of diastereomeric deviation is 3.5 at 360 K for rate constants and as high as 1.6 for mechanism reactivity, in terms of ignition delay times, as opposed to a mechanism without stereochemical expansion.

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

Nanomechanical sampling of material for nanoscale mass spectrometry chemical analysis

The ability to spatially resolve the chemical distribution of compounds on a surface is important in many applications ranging from biological to material science. To this extent, we have recently introduced a hybrid atomic force microscopy (AFM)-mass spectrometry (MS) system for direct thermal desorption and pyrolysis of material with nanoscale chemical resolution. However, spatially resolved direct surface heating using local thermal desorption becomes challenging on material surfaces with low melting points, because the material will undergo a melting phase transition due to heat dissipation prior to onset of thermal desorption. Therefore, here we developed an approach using mechanical sampling and collection of surface materials on an AFM cantilever probe tip for real-time analysis directly from the AFM tip. This approach allows for material to be concentrated directly onto the probe for subsequent MS analysis. We evaluate the performance metrics of the technique and demonstrate localized MS sampling from a candelilla wax matrix containing UV stabilizers avobenzone and oxinoxate from areas down to 250 nm × 250 nm. Overall, this approach removes heat dissipation into the bulk material allowing for a faster desorption and concentration of the gas phase analyte from a single heating pulse enabling higher signal levels from a given amount of material in a single sampling spot.

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

Effects of long-term elevated CO 2 treatment on the inner and outer bark chemistry of sweetgum (Liquidambar styraciflua L.) trees

Long-term exposure of sweetgum trees to elevated atmospheric CO 2 concentrations significantly shifted inner bark (phloem) and outer bark (rhytidome) chemical compositions, having implications for both defense and nutrient cycling. Changes in plant tissue chemistry due to increasing atmospheric carbon dioxide (CO 2 ) concentrations have direct implications for tissue resistance to abiotic and biotic stress while living, and soil nutrient cycling when senesced as litter. Although the effects of elevated CO 2 concentrations on tree foliar chemistry are well documented, the effects on tree bark chemistry are largely unknown. The objective of our study was to determine the effects of a long-term elevated CO 2 treatment on the contents of individual elements, extractives, ash, lignin, and polysaccharide sugars of sweetgum (Liquidambar styraciflua L.) bark. Trees were harvested from sweetgum plots equipped with the Free-Air CO 2 Enrichment (FACE) apparatus, receiving either elevated or ambient CO 2 treatments over a 12-year period. Whole bark sections were partitioned into inner bark (phloem) and outer bark (rhytidome) samples before analysis. Moreover, principal component analysis, coupled with either Fourier transform infrared spectroscopy or pyrolysis-gas chromatography-mass spectrometry data, was also used to screen for differences. Elevated CO 2 reduced the N content (0.42 vs. 0.35 %) and increased the C:N ratio (109 vs. 136 %) of the outer bark. For the inner bark, elevated CO 2 increased the Mn content (470 vs. 815 mg kg -1 ), total extractives (13.0 vs. 15.6 %), and residual ash content (8.1 vs. 10.8 %) as compared to ambient CO 2 ; differences were also observed for some hemicellulosic sugars, but not lignin. Shifts in bark chemistry can affect the success of herbivores and pathogens in living trees, and as litter, bark can affect the biogeochemical cycling of nutrients within the forest floor. Our results demonstrate that increasing atmospheric CO 2 concentrations have the potential to impact the chemistry of temperate, deciduous tree bark such as sweetgum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Evolution of N-Coordinated Iron–Carbon (FeNC) Catalysts and Their Oxygen Reduction (ORR) Performance in Acidic Media at Various Stages of Catalyst Synthesis: An Attempt at Benchmarking

The objective of this study was to understand the role of iron and the heat treatment steps involved in nitrogen-coordinated iron-carbon (FeNC) catalyst synthesis. We have studied the oxygen reduction reaction (ORR) performance of these catalysts as they evolve from their most crude and inactive form to their most active form. Electrochemical half-cell and fuel cell tests suggest that the presence of Fe was crucial in these samples. The high-temperature heat treatment (once in argon and then in ammonia) at temperatures ≥950 °C were also critical in imparting these catalysts with their highest activity; however, significant loss of activity was observed with cycling and potential hold at 0.5 V for 100 h. In addition, acid-washing after the first or the second pyrolysis steps produced a marked decrease in ORR activity relative to their unwashed counterparts. We also report findings from our efforts towards benchmarking FeNC catalysts for oxygen reduction reaction electrocatalysis. Specifically, we focus on correlating the specific kinetic current (iK) at 0.75 V to electrochemically accessible surface area (EASA) and roughness factor (RF) determined from electrochemical double layer capacitance measurements. 57 Fe Mössbauer spectroscopy was employed to shed light into the nature of active sites in FeNC catalysts and provide insights into their deactivation behavior caused by acid-washing. The results suggest planar FeN 4 doublet (Fe 2+ , low spin) as an active site in these materials, which may be leached away in acid, explaining their decreased activity after acid washing. Results for characterization experiments using X-ray photoelectron spectroscopy, temperature programmed oxidation and X-ray absorption spectroscopy, superconducting quantum interference device magnetometry are also presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Properties of Poly(Vinyl Alcohol)/Chitosan Nanocomposite Films Reinforced with Oil Palm Empty Fruit Bunch Amorphous Lignocellulose Nanofibers

The objective of this study was to investigate the properties of poly(vinyl alcohol)/chitosan nanocomposite films reinforced with different concentration of amorphous LCNFs. The properties analyzed were morphological, physical, chemical, thermal, biological, and mechanical characteristics. Oil palm empty fruit bunch LCNFs obtained from multi-mechanical stages were more dominated by amorphous region than crystalline part. Varied film thickness, swelling degree, and transparency of PVA/chitosan nanocomposite films reinforced with amorphous part were produced. Aggregated LCNFs, which reinforced PVA/chitosan polymer blends, resulted in irregular, rough, and uneven external surfaces as well as protrusions. Based on XRD analysis, there were two or three imperative peaks that indicated the presence of crystalline states. The increase in LCNFs concentration above 0.5% to PVA/chitosan polymer blends led to the decrease in crystallinity index of the films. A noticeable alteration of FTIR spectra, which included wavenumber and intensity, was obviously observed along with the inclusion of amorphous LCNFs. That indicated that a good miscibility between amorphous LCNFs and PVA/chitosan polymer blend generated chemical interaction of those polymers during physical blending. Reinforcement of PVA/chitosan polymer blends with amorphous LCNFs influenced the changes of T{sub g} (glass transition temperature), T{sub m} (melting point temperature), and T{sub max} (maximum degradation temperature). Three thermal phases of PVA/chitosan/LCNFs nanocomposite films were also observed, including absorbed moisture evaporation, PVA and chitosan polymer backbone structural degradation and LCNFs pyrolysis, and by-products degradation of these polymers. The addition of LCNFs 0.5% had the highest tensile strength and the addition of LCNFs above 0.5% decreased the strength. The incorporation of OPEFB LCNFs did not show anti-microbial and anti-fungal properties of the films. The addition of amorphous LCNFs 0.5% into PVA/chitosan polymer blends resulted in regular and smooth external surfaces, enhanced tensile strength, increased crystallinity index, and enhanced thermal stability of the films.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Effect of Annealing Temperature on Structural, Morphological, Optical and Magnetic Properties of NiFe{sub 2}O{sub 4} Thin Films

Nickel ferrite (NiFe{sub 2}O{sub 4}) thin films have been deposited on glass substrates by a chemical spray pyrolysis technique at 350 {sup ∘}C substrate temperature. The deposited films were annealed at four different temperatures (400, 450, 500 and 550 {sup ∘}C), and the effect of annealing temperature on the structural, morphological, optical and magnetic properties were studied. The annealed films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), UV-visible spectroscopic analysis and vibrating sample magnetometer (VSM). XRD patterns showed that the NiFe{sub 2}O{sub 4} is oriented along (311) plane, which enhances peak intensity with respect to the annealing temperature. The analysis of XRD pattern revealed the formation of single-phase cubic spinel structure. The FT-IR spectrum of NiFe{sub 2}O{sub 4} thin films showed strong absorption peaks around 616 and 353 cm{sup − 1} which indicates the cubic spinel crystal structure of the films. FE-SEM micrographs show that the grain size increases with an increase in annealing temperature. The grain size varies between ∼ 19 and ∼ 28 nm, confirming the nanocrystalline nature of the prepared thin films. The optical properties of the films were studied by an absorbance spectrum in the range of 300 to 800 nm. The results showed that the energy band gap decreased with the increase of annealing temperature. Magnetic properties of NiFe{sub 2}O{sub 4} thin films exhibit a strong dependence on the annealing temperature. The saturation magnetization increases from ∼ 68.29 to ∼ 205.24 emu/cm{sup 3} with increasing annealing temperature, which is in favour of modern electronic device miniaturization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Characterization of Deactivated Bio-oil Hydrotreating Catalysts

Deactivation of bio-oil hydrotreating catalysts remains a significant challenge because of the poor quality of pyrolysis bio-oil input for hydrotreating and understanding their deactivation mode is critical to developing improved catalysts and processes. In this research, we developed an understanding of the deactivation of two-step bio-oil hydrotreating catalysts (sulfided Ru/C and sulfided CoMo/C) through detailed characterization of the catalysts using various complimentary analytical techniques. Severe fouling of both catalysts by carbonaceous species was the major form of deactivation, which is consistent with the significant loss of surface area and pore volume of both deactivated catalysts and the significant increase of the bulk density. Further analysis of the carbonaceous species by thermogravimetric analysis and x-ray photoelectron spectroscopy indicated that the carbonaceous species was formed by condensation reaction of active species such as sugars and sugar derivatives (aldehydes and ketones) in bio-oil feedstock during bio-oil hydrotreating under the conditions and catalysts used. Microscopy results did not show metal sintering of the Ru/C catalyst. However, X-ray diffraction indicated a probable transformation of the highly-active CoMoS phase in the sulfided CoMo/C catalyst to Co8S9 and MoS2 phase with low activity. Loss of the active site by transport of inorganic elements from the bio-oil and the reactor construction material onto the catalyst surface also might be a cause of deactivation as indicated by elemental analysis of spent catalysts.

bio-oil hydrotreating↗
DOE OSTI2019

Oxidation and Ignition Behaviors of Molten Mg-Nd-Zr Alloy in Resin-Sand Mold

High-temperature oxidation behavior of molten Mg-Nd-Zr in the pyrolysis atmosphere of resin-bind sand mold was investigated. The results showed that pouring temperature higher than 1023 K would sharply increase the ignition risk of melt in mold. The oxide formed on Mg-Nd-Zr melt below 973 K consists of two layers: mainly MgO for outer layer; mixture of MgO and Nd{sub 2}O{sub 3} for inner layer. The inner oxide mixture layer played an essential role in the protection of Mg-Nd-Zr matrix. Based on the experimental results and thermodynamic analysis, the oxidation process containing three stages was proposed. Nd- and Zn-enriched zone was found at the subsurface of oxide scale, without the enrichment of Zr. DICTRA calculation results indicated that this phenomenon was caused by the depletion of Mg and up-hill diffusion of Zr. Thus, Zr showed limited protection to the melt in long-term oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

An Eco-Friendly System for the Production of Value-Added Materials from Dairy Manure

A technoeconomic model has been developed to explore the viability of a two-stage anaerobic digester (AD) coupled with additional processes to increase the economic attractiveness of a new manure treatment system. The addition of a polyhydroxyalkanoate (PHA) reactor, algae cultivation system (ACS), and a biomass treatment system, such as, fast-pyrolysis or hydrothermal liquefaction (HTL) would further sequester carbon and nutrients, as well as add valuable products that can be sold or used on-site to mitigate costs. The Decision-support for Digester-Algae IntegRation for Improved Environmental and Economic Sustainability (DAIRIEES) model is used to evaluate the effectiveness and viability of this system to achieve economic and environmental sustainability by the dairy industry. The DAIRIEES model was used to evaluate the effectiveness and viability of this system to achieve economic viability and environmental sustainability by the dairy industry. A base case with mass flows and economics for a 10,000 herd dairy is considered. The integrated manure treatment system can reduce the amount of nitrogen released from the manure by 61.7%. If the ACS is not incorporated into the system, the nitrogen reduction drops to 19%. Similarly, the amount of phosphorus available for release to the environment is reduced by 37.4% with the full system, and by 26% for the system without the ACS. The results of the economic analysis indicate a net loss for the integrated system with algae cultivation. Without algae cultivation, the manure treatment system is profitable with a payback period of less than five years.

09 BIOMASS FUELS↗
DOE OSTI2016

Cell Wall Composition and Underlying QTL in an F1 Pseudo-Testcross Population of Switchgrass

Natural genetic variation for reduced recalcitrance can be used to improve switchgrass for biofuel production. A full-sib switchgrass mapping population developed by crossing a lowland genotype, AP13, and upland genotype, VS16, was evaluated at three locations (Ardmore and Burneyville, OK and Watkinsville, GA). Biomass harvested after senescence in 2009 and 2010 was evaluated at the National Renewable Energy Laboratory (NREL) for sugar release using enzymatic hydrolysis and for lignin content and syringyl/guaiacyl lignin monomer (S/G) ratio using pyrolysis molecular beam mass spectrometry (py-MBMS). Glucose and xylose release ranged from 120 to 313 and 123 to 263 mg g -1 , respectively, while lignin content ranged from 19 to 27% of the dry biomass. Statistically significant differences were observed among the genotypes and the environments for the cell wall composition traits. Regression analysis showed that a unit increase in lignin content reduced total sugar release by an average of 10 mg g -1 . Quantitative trait loci (QTL) analysis detected 9 genomic regions underlying sugar release and 14 for lignin content. The phenotypic variation explained by the individual QTL identified for sugar release ranged from 4.5 to 9.4 and for lignin content from 3.8 to 11.1%. Mapping of the QTL regions to the switchgrass genome sequence (v1.1) found that some of the QTL colocalized with genes involved in carbohydrate processing and metabolism, plant development, defense systems, and transcription factors. Finally, the markers associated with QTL can be implemented in breeding programs to efficiently develop improved switchgrass cultivars for biofuel production.

09 BIOMASS FUELS↗