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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 1,603 records · Page 89

Hierarchically Structured Catalysts Toward Sustainable Hydrogen Economy: Electro‐ and Thermo‐Chemical Pathways

Abstract Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero‐emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low‐carbon energy solutions. Thermochemical catalysis process dominates hydrogen production at scale given its relatively mature technology and commercialization status, as well as the established manufacturing infrastructure. While due to its environmentally friendly nature and growing abundant sources of renewable electricity, the electrochemical path for hydrogen production is rising as a major alternative to the thermochemical means. Nevertheless, hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancement of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro‐ and thermo‐ chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt‐group metal (PGM) and non‐PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high‐level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Deng, Chenxin↗

Benzimidazolone-Dioxazine Pigments-Based Conjugated Polymers for Organic Field-Effect Transistor

Molecules based on benzimidazolone-dioxazine are known as blue/violet pigments and have been commercialized for decades. However, unfavorable solubility limits the application of these structures as building blocks of conjugated polymers despite their low band gaps. Herein, a series of donor–acceptor conjugated polymers containing soluble benzimidazolone-dioxazine structures as the acceptors and oligothiophene as donors are synthesized and investigated. With increasing numbers of thiophene rings, the steric hindrance diminishes and high molecular weight polymers can be achieved, leading to an improved performance in organic field effect transistor devices. The hole mobility of polymers with three to six thiophene units is in the order of 10 -1 cm2 V -1 s -1 . Among all the polymers, polymer P3 with three thiophene units between benzimidazolone-dioxazine structures shows the best hole mobility of 0.4 cm2 V -1 s -1 . Grazing-incidence wide-angle X-ray scattering results reveal that the high mobility of organic field-effect transistors (OFETs) can be accredited by matched donor–acceptor packing in the solid thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bioenergy Underground: Challenges and opportunities for phenotyping roots and the microbiome for sustainable bioenergy crop production

Abstract Bioenergy production often focuses on the aboveground feedstock production for conversion to fuel and other materials. However, the belowground component is crucial for soil carbon sequestration, greenhouse gas fluxes, and ecosystem function. Roots maximize feedstock production on marginal lands by acquiring soil resources and mediating soil ecosystem processes through interactions with the microbial community. This belowground world is challenging to observe and quantify; however, there are unprecedented opportunities using current methodologies to bring roots, microbes, and soil into focus. These opportunities allow not only breeding for increased feedstock production but breeding for increased soil health and carbon sequestration as well. A recent workshop hosted by the USDOE Bioenergy Research Centers highlighted these challenges and opportunities while creating a roadmap for increased collaboration and data interoperability through standardization of methodologies and data using F.A.I.R. principles. This article provides a background on the need for belowground research in bioenergy cropping systems, a primer on root system properties of major U.S. bioenergy crops, and an overview of the roles of root chemistry, exudation, and microbial interactions on sustainability. Crucially, we outline how to adopt standardized measures and databases to meet the most pressing methodological needs to accelerate root, soil, and microbial research to meet the pressing societal challenges of the century.

09 BIOMASS FUELS↗

2D HSQC Chemical Shifts of Impurities from Biomass Pretreatment

Two dimensional (2D) heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) is a powerful analytical method which can be used to elucidate the structure of biomass. During processing, biomass is typically subjected to some form of chemical treatment which can be performed with a variety of compounds. The presence of these compounds, even in trace amounts, has the potential to contaminate the sample and lead to misinterpretation of the HSQC spectra. Here we report the chemical shifts of 29 compounds commonly used in biomass processing which have the potential to contaminate the biomass samples and lead to the misinterpretation of peaks associated with biomass (Populus trichocarpa ) pretreated via autohydrolysis. The identification of these chemical shifts could serve as a valuable tool in preventing errors in characterizing biomass via HSQC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water-Pillared Sodium Vanadium Bronze Nanowires for Enhanced Rechargeable Magnesium Ion Storage

Owing to the advantages of high safety, low cost, high theoretical volumetric capacities, and environmental friendliness, magnesium-ion batteries (MIBs) have more feasibility for large-scale energy storage compared to lithium-ion batteries. However, lack of suitable cathode materials due to sluggish kinetics of magnesium ion is one of the biggest challenges. Herein, water-pillared sodium vanadium bronze nanowires (Na 2 V 6 O 16 ·1.63H 2 O) are reported as cathode material for MIBs, which display high performance in magnesium storage. The hydrated sodium ions provide excellent structural stability. The charge shielding effect of lattice water enables fast Mg 2+ diffusion. It exhibits high specific capacity of 175 mAh g -1 , long cycle life (450 cycles), and high coulombic efficiency (≈100%). At high current density of 200 mA g -1 , the capacity retention is up to 71% even after 450 cycles (compared to the highest capacity), demonstrating excellent long-term cycling performance. The nature of charge storage kinetics is explored. Furthermore, a highly reversible structure change during the electrochemical process is proved by comprehensive electrochemical analysis. The remarkable electrochemical performance makes Na 2 V 6 O 16 ·1.63H 2 O a promising cathode material for low-cost and safe MIBs.

36 MATERIALS SCIENCE↗

Measuring Biomass-Derived Products in Biological Conversion and Metabolic Process

Biomass can be converted to various types of products in biological and metabolic processes. For an in-depth understanding of biomass conversion, quantitative and qualitative information of products in these conversion processes are essential. Here we introduce analytical techniques including high-performance liquid chromatography (HPLC), gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), and nuclear magnetic resonance (NMR) for biomass-based products characterization in biological and metabolic processes.

Yoo, Chang Geun↗

Establishing performance metrics for quantitative non-targeted analysis: a demonstration using per- and polyfluoroalkyl substances

Abstract Non-targeted analysis (NTA) is an increasingly popular technique for characterizing undefined chemical analytes. Generating quantitative NTA (qNTA) concentration estimates requires the use of training data from calibration “surrogates,” which can yield diminished predictive performance relative to targeted analysis. To evaluate performance differences between targeted and qNTA approaches, we defined new metrics that convey predictive accuracy, uncertainty (using 95% inverse confidence intervals), and reliability (the extent to which confidence intervals contain true values). We calculated and examined these newly defined metrics across five quantitative approaches applied to a mixture of 29 per- and polyfluoroalkyl substances (PFAS). The quantitative approaches spanned a traditional targeted design using chemical-specific calibration curves to a generalizable qNTA design using bootstrap-sampled calibration values from “global” chemical surrogates. As expected, the targeted approaches performed best, with major benefits realized from matched calibration curves and internal standard correction. In comparison to the benchmark targeted approach, the most generalizable qNTA approach (using “global” surrogates) showed a decrease in accuracy by a factor of ~4, an increase in uncertainty by a factor of ~1000, and a decrease in reliability by ~5%, on average. Using “expert-selected” surrogates ( n = 3) instead of “global” surrogates ( n = 25) for qNTA yielded improvements in predictive accuracy (by ~1.5×) and uncertainty (by ~70×) but at the cost of further-reduced reliability (by ~5%). Overall, our results illustrate the utility of qNTA approaches for a subclass of emerging contaminants and present a framework on which to develop new approaches for more complex use cases. Graphical Abstract

Pu, Shirley (ORCID:0000000201223797)↗

Deuterium incorporation into cellulose: a mini-review of biological and chemical methods

Isotopic enrichment offers structural insights that are not easily accessible with natural abundance isotopic composition. Deuterated cellulose has attracted considerable attention in the field of neutron scattering studies, providing information about the dynamics, structure of cellulose and its interactions with other plant cell wall components. The deuteration of cellulose also allows the analysis of cellulose hydrogen bonds by FTIR or NMR techniques. The chemical structure of cellulose contains both exchangeable hydroxyl and non-exchangeable alkyl hydrogens. Deuterium incorporation can be divided into two classifications: biological route which incorporates both alkyl and hydroxyl bound deuterium, and chemical route which typically replaces hydroxyl-bound exchangeable hydrogen. Additionally, the biological route involves cultivating plants or microorganisms in a deuterium-enriched medium. The chemical route typically involves an exchange reaction between hydroxyl-bound hydrogen and D 2 O, often facilitating with an alkaline reagent. This review provides an overview of recent advances in deuteration methods and characterization as well as the application of deuterated cellulose.

59 BASIC BIOLOGICAL SCIENCES↗

Functional group effect of chemically modified microcrystalline methyl cellulose on thermoplastic polyurethane composites

Microcrystalline cellulose (MCC) is a promising bio-based filler for lightweight yet mechanically high-performance eco-polymer composites because of its low density and high biocompatibility. However, intermolecular hydrogen bonding among MCC is stronger than the polymer–filler interactions, which deteriorate the mechanical properties of the composites. Herein, we investigated the effects of functional groups on the mechanical properties of composites by scrutinizing chemically modified microcrystalline methyl cellulose (m-MMC) with three different substitution levels of hydroxyl group to hydroxypropyl (HP) group: no-, low-, and high-level substitution (HP-0, HP-low, and HP-high). The degree of HP substitution of m-MMC was quantitatively measured by CP/MAS NMR analysis. The relatively bulky HP groups interrupted the filler–filler intermolecular interactions and reduced the crystallinity and density of m-MMC, as evident from X-ray diffractometer and pycnometer data, respectively. For scalable production of the composites, the m-MMC were compounded with thermoplastic polyurethane (TPU) by a twin-screw extruder at concentrations between 0.5 and 10 wt%. Despite its low filler concentration, the toughness of m-MMC/TPU composites was remarkably enhanced, up to 28% (229.2 to 294.4 MJ/m 3 ) at 0.5 wt% loading of HP-low, owing to the enhanced polymer–filler interactions. In conclusion, the fundamental understanding on structure–property relationships will provide insights for designing of mechanically robust yet eco-friendly polymer composites.

composites↗

Hydrogen bond–induced aqueous-phase surface modification of nanocellulose and its mechanically strong composites

Aqueous-phase surface modification of nanocellulose is desirable because nanocellulose is generally produced via water-based fibrillation. In this study, a hydrogen bond–induced surface modification of cellulose nanofibrils (CNFs) in water was developed. Tannic acid and polyvinylpyrrolidone were chosen to modify the CNFs because of their strong capacity for hydrogen bond formation. By tuning the hydrogen bond formation between CNFs, tannic acid, and polyvinylpyrrolidone, CNFs with different surface hydrophilicity were achieved. Additionally, the modified CNFs can assemble into strong and tough composites owing to the hydrogen bond network in the system. Modified CNFs demonstrated 76% higher tensile strength and 100% higher toughness than those of unmodified CNFs, reaching 162 MPa and 12.7 MJ/m 3 , respectively. This study provides a new water-based modification strategy for the nanocellulose, leading the way toward producing strong nanocellulose composites via noncovalent interaction.

36 MATERIALS SCIENCE↗

Unveiling mechanism of surface-guided platinum nanowire growth

We report surface-guided growth of non-planar nanowires on functional substrates offers the new opportunity to precisely control their diameter, length, density and alignment, which will greatly benefit their direct integration into practical devices for large-scale applications. However, control of noble metal nanowires growth and arrangement remains a great challenge, and the mechanistic understanding is still limited. Herein, we choose Pt as a model material system to study the synthesis conditions required to control the in situ growth of aligned Pt nanowires on flat titanium substrate via a one-step and room-temperature green chemical synthesis process in aqueous solution. Most importantly, it is for the first time discovered that ordered nanoarrays and self-assembled nanoflowers can be directly grown on flat Ti substrate by merely adjusting the reaction times, without use of any soft/hard templates, surfactants and organic solvents. The proposed surface-guided growth mechanisms for nanoarray and nanoflower formation in this study may shed light on understanding of oriented arrangement/assembly of one-dimensional Pt nanowires into desirable morphologies for a variety of practical device applications.

Pt nanoflower↗

Meso-Scale Electrodynamic Coupling of the Earth Magnetosphere-Ionosphere System

Within the fully integrated magnetosphere-ionosphere system, many electrodynamic processes interact with each other. We review recent advances in understanding three major meso-scale coupling processes within the system: the transient field-aligned currents (FACs), mid-latitude plasma convection, and auroral particle precipitation. (1) Transient FACs arise due to disturbances from either dayside or nightside magnetosphere. As the interplanetary shocks suddenly compress the dayside magnetosphere, short-lived FACs are induced at high latitudes with their polarity successively changing. Magnetotail dynamics, such as substorm injections, can also disturb the current structures, leading to the formation of substorm current wedges and ring current disruption. (2) The mid-latitude plasma convection is closely associated with electric fields in the system. Recent studies have unraveled some important features and mechanisms of subauroral fast flows. (3) Charged particles, while drifting around the Earth, often experience precipitating loss down to the upper atmosphere, enhancing the auroral conductivity. Recent studies have been devoted to developing more self-consistent geospace circulation models by including a better representation of the auroral conductance. It is expected that including these new advances in geospace circulation models could promisingly strengthen their forecasting capability in space weather applications. The remaining challenges especially in the global modeling of the circulation system are also discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Amorphous Iridium Oxide-Integrated Anode Electrodes with Ultrahigh Material Utilization for Hydrogen Production at Industrial Current Densities

Herein, ionomer-free amorphous iridium oxide (IrO x ) thin electrodes are first developed as highly active anodes for proton exchange membrane electrolyzer cells (PEMECs) via low-cost, environmentally friendly, and easily scalable electrodeposition at room temperature. Combined with a Nafion 117 membrane, the IrO x -integrated electrode with an ultralow loading of 0.075 mg cm –2 delivers a high cell efficiency of about 90%, achieving more than 96% catalyst savings and 42-fold higher catalyst utilization compared to commercial catalyst-coated membrane (2 mg cm –2 ). Additionally, the IrO x electrode demonstrates superior performance, higher catalyst utilization and significantly simplified fabrication with easy scalability compared with the most previously reported anodes. Notably, the remarkable performance could be mainly due to the amorphous phase property, sufficient Ir 3+ content, and rich surface hydroxide groups in catalysts. Overall, due to the high activity, high cell efficiency, an economical, greatly simplified and easily scalable fabrication process, and ultrahigh material utilization, the IrO x electrode shows great potential to be applied in industry and accelerates the commercialization of PEMECs and renewable energy evolution.

08 HYDROGEN↗

Nanoarray-Based Monolithic Adsorbers for SO 2 Removal

Nanoarray-based monolithic catalysts have been developed for various applications, including CO oxidation, hydrocarbon combustion, lean NO x trapping, and low-pressure CO 2 hydrogenation. In this work, SO 2 adsorption properties have been explored and evaluated on the cordierite honeycomb monoliths grown with zinc oxide nanoarray (ZnO), zinc oxide nanoarray washcoated by BaCO 3 nanoparticles (ZnO/BaCO 3 ), and manganese oxide nanowire array with cryptomelane structure (MnO x ) at a temperature range from 50 to 425 °C. All samples show temperature-dependent SO 2 adsorption behaviors. The adsorption results reveal the performance order: MnO x > ZnO/BaCO 3 > ZnO, with ~ 90% SO 2 adsorbed in MnO x at 425 °C. Washcoated BaCO 3 contributes to the improvement of SO 2 adsorption in ZnO nanoarray, and the best performance displayed in MnO x may be attributed to their high specific surface area. After regeneration, nanoarrays all exhibit good thermal stability during test-regeneration cycles. No additional phase is formed in regenerated ZnO nanoarrays (ZnO-R), while BaCO 3 is converted to BaSO 4 in the regenerated ZnO/BaCO 3 nanoarrays (ZnO/BaCO 3 -R), and the sulfur species (possibly MnSO 4 ) and Mn 2 O 3 are found in regenerated MnO x nanoarrays (MnO x -R). It is noted that a small amount of sulfur species (possibly MnSO 4 ) may promote the SO 2 adsorption of MnO x -R at a lower temperature, while the formed Mn 2 O 3 contributes to the deactivation of MnO x -R.

36 MATERIALS SCIENCE↗

Biochar–polymer composites for 3D printing: a review

Biochar, a bio-based co-product of biofuel production via thermochemical conversion, holds potential as a filler for polymer composites to reduce costs, improve thermomechanical properties, and aid in environmental remediation. 3D-printed biochar composites have received growing interest over the past few years but have experienced difficulties such as poor layer adhesion and nozzle clogging. Currently, no literature review examines 3D-printed biochar composites and related biochar properties in-depth. This work summarizes and discusses recent studies on 3D-printed polymer and biochar composites and examines their mechanical, thermal, and additional properties that result from each study. Technical challenges in printability, such as nozzle clogging from particle size and biochar aggregation, are also discussed. Furthermore, this work discusses the variability of biochar properties resulting from the pyrolysis conditions and feedstock choice in relation to potential 3D printing outcomes. In particular, several studies reported that high lignin feedstocks could be candidates for 3D printing. The post-processing approaches of the biochar via physical and chemical methods are also introduced. Ball milling appears to hold the most promise for physical treatments due to its tunability of particle size, surface area, and functional groups, while chemical treatments with acids or alkalis are used to tailor biochar porosity and wettability. Overall, it was determined that future research needs to be done relating biochar production and post-processing methods to resulting 3D printing parameters as the number of studies is limited.

Day, Rachel [Auburn University, Auburn, AL]↗

Post-irradiation examination of the Sirius-1 nuclear thermal propulsion fuel test

Nuclear Thermal Propulsion (NTP) systems hold promise in reducing transit times for exploration of the solar system by both crewed and uncrewed missions. NTP systems currently under investigation include a once-through high-temperature gas-cooled fission reactor to provide thermal energy to heat the coolant, which also serves as the propellant. The fuel system consists of angular UN fuel particles dispersed in a matrix of W/Re, creating a ceramic and metallic composite or cermet, which has been irradiated in Idaho National Laboratory's (INL) Transient Reactor Test Facility (TREAT). This enabled evaluation of these materials under representative nuclear heating rates (~95 K/s) and peak surface temperatures (~2527 K). Further, these surface conditions were indicative of achievement of the target peak internal temperature of approximately 2850 K. These tests named Sirius-1 (UN–W/Re), have been irradiated and this paper will present post-irradiation examination results. The Sirius-1 test produced minor, stable cracks in the fuel specimen and spalling of surface material. Volatilized uranium ‘soot’ was found deposited on the inner wall of the irradiation capsule indicating loss of some fissile material from the fuel specimen. Spalling from the surfaces was also noted upon visual inspection. Uranium diffusion from the fuel particles resulted in the formation of U/Re phases and the production of a laminar microstructure on the edge of the fuel system. Overall, the specimen was stable and remained within a coolable geometry upon conclusion of multiple thermal cycles to prototypical operating temperatures.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗