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At least 757 records · Page 42

Opportunities and Challenges for Hydrotreating of Catalytic Fast Pyrolysis Oil to Fuels

Catalytic fast pyrolysis (CFP) provides a versatile platform for producing fuels to combat climate change and meet decarbonizing targets. In this contribution, we will discuss the hydroprocessing of CFP oils to a variety of fuels, including sustainable aviation fuel (SAF), diesel, and marine fuel. Both standalone and co-hydroprocessing with petroleum streams will be covered. Hydrotreating CFP oil at temperatures around 400 Degrees Celsius can produce a highly deoxygenated product with oxygen contents below the detection limit. However, the quality of fuel fractions produced has been a problem, manifesting as low octane numbers for the gasoline-range fraction and low cetane numbers for the diesel-range fraction. Incorporating an initial transition zone for hydrogenation during hydrotreating was shown to dramatically increase the diesel fraction cetane number from 24 to 45. A similar approach enabled the production of a cycloalkane-rich SAF fraction meeting key ASTM 4054 guidelines with respect to density, viscosity, heating value, volatility, freeze and flash point. Over 400 hours of hydrotreating for SAF was demonstrated with no signs of catalyst bed fouling, measured by pressure drop over the catalyst bed. Compared to other fuels, marine fuel is unique in that it does not require complete deoxygenation. We investigated the minimum hydrotreating requirements to produce fuel compatible with very low sulfur fuel oil, and the results suggested 30% reduction in hydrotreating costs for this approach. Co-hydroprocessing offers an opportunity to take advantage of refinery infrastructure and economies of scale although the operation is less flexible with respect to operating conditions. Co-hydroprocessing CFP oil with petroleum streams gave efficient deoxygenation at milder conditions (e.g. at temperatures of 320 Degrees Celsius) than required for standalone hydrotreating. Over 90% incorporation of biogenic carbon in the CFP oil was confirmed by carbon-14 analysis. Hydrotreating of CFP oil, whether by standalone or co-processing, can produce a variety of fuel cuts, whose quality can be tailored by changing process conditions. Challenges remain, including long-term catalyst performance and determining CFP oil quality requirements.

09 BIOMASS FUELS↗

Applicability of Electrical and Electroanalytical Techniques to Detect Water and Characterize the Geochemistry of Undisturbed Planetary Soils

The search for life is a primary goal of NASA s planetary exploration program. The search is, of necessity, tiered in both the detection approach (looking for evidence of microbial fossils or the presence of water in the geological history of a planetary body and/or looking for evidence of water, energy sources, precursors to life, signatures of life and/or life itself in the present day planetary environment) and in the survey method (scale, range, specificity) employed. Terrestrial investigations suggests that life as we know it requires water. Thus, the search for extant microbial life and habitats requires identifying water-bearing soils. Determining Reduction-Oxidation (REDOX) couples present in water, once it is found, provides information on soil geochemistry and identifies potential chemical energy sources for life. Mars offers a near-term target for conducting this search. The identification of gully formation [1], layered deposits [2] and elemental ratios of bromine and chlorine [3] present indirect evidence that water was abundant locally in the Martian past. Additionally, Viking images of polar ice and frost formation on the surface of Mars demonstrate that water can exist in at least some near-surface regions of present-day Mars. Atmospheric pressure data further suggest that liquid water may be stable for short periods of time in the mid-latitudes of the Martian surface. [4] Measurements of the global distribution of hydrogen in the Martian regolith offer tantalizing indirect evidence that water may at least exist in near-surface soils. [5] Evidently, any water to be found is likely to exist as soil mixtures at levels ranging between approx.0.5% and approx.5 %.

Seshadri, S.↗

Hydrothermal catalytic conversion of oleic acid to heptadecane over Ni/ZrO 2

There is growing interest in the substitution of expensive noble metal catalysts with low-cost earth-abundant metals in applications targeting biofuels production from waste organic feedstocks. Here, nickel (Ni) catalysts supported on zirconium dioxide (ZrO 2 ), both with and without copper (Cu) as a co-metal, were tested in hydrothermal reactions of unsaturated and saturated C18 fatty acids as models for waste oil feedstocks. In contrast to recent reports, this study showed no enhancement of nickel's activity for fatty acid conversion to alkane products when Cu was present. Ni/ZrO 2 prepared by metal coprecipitation methods converted 100% of oleic acid with 25% selectivity to heptadecane after 5h of reaction at 350 °C using methanol as a hydrogen donor source, increasing to 41% heptadecane after 20 h. Lower yields were observed with catalysts prepared by wet impregnation and using alternative hydrogen donor sources (glycerol, formic acid). Greater selectivity to heptadecane was also observed at higher temperatures (370 °C) and when the initial fatty acid had greater saturation. Longer term exposure to hydrothermal media led to metal sintering and catalyst deactivation. Findings support a path forward to the development of earth-abundant metal catalysts for the upgrading of waste organic feedstocks.

09 BIOMASS FUELS↗

Motion of Molecules in Supramolecular Scaffolds Enhances Bone Regeneration

The regeneration of human tissues is a great scientific challenge and a critical factor to achieve a long healthspan and prevent disabilities due to injury or disease. Materials chemistry can contribute to this goal with the development of bioactive supramolecular systems that can signal cells for regeneration. Recent work in our laboratory using in vivo models of spinal cord injury and cartilage regeneration has demonstrated that the motion of bioactive molecules in supramolecular scaffolds enhances receptor signaling. We report here on a novel molecular strategy to control supramolecular motion in filamentous assemblies using bone regeneration as a functional target. The supramolecular assemblies are composed of monomers that arrange, by design, with either parallel or antiparallel β-sheets, and some of them contain a terminal peptide sequence that binds BMP-2. We found that parallel β-sheet supramolecular assemblies promote greater osteogenic differentiation of progenitor cells in vitro relative to antiparallel assemblies, as well as superior quality of newly regenerated bone in a rat model of spinal fusion. Furthermore, these assemblies drastically reduce the dangerous supraphysiological dose of BMP-2 used clinically for spinal fusion. Here, we attribute the enhanced bioactivity to the weaker nature of hydrogen bonds in parallel relative to antiparallel β-sheet assemblies, which in turn allows greater supramolecular motion and cell signaling of the growth factor-binding molecules.

Anatomy↗

Long-Term Cryogenic Propellant Storage for the TOPS Mission

Cryogenic propellants such as liquid hydrogen (LH2) and liquid oxygen (LOX) can dramatically enhance NASAs ability to explore the solar system because of their superior specific impulse (Isp) capability. Although these cryogenic propellants can be challenging to manage and store, they allow significant mass advantages over traditional hypergolic propulsion systems and are therefore technically enabling for many planetary science missions. New cryogenic storage techniques such as subcooling and the use of advanced insulation and low thermal conductivity support structures will allow for the long term storage and use of cryogenic propellants for solar system exploration and hence allow NASA to deliver more payloads to targets of interest, launch on smaller and less expensive launch vehicles, or both. Employing cryogenic propellants will allow NASA to perform missions to planetary destinations that would not be possible with the use of traditional hypergolic propellants. These new cryogenic storage technologies were implemented in a design study for the Titan Orbiter Polar Surveyor (TOPS) mission, with LH2 and LOX as propellants, and the resulting spacecraft design was able to achieve a 43 launch mass reduction over a TOPS mission, that utilized a conventional hypergolic propulsion system with mono-methyl hydrazine (MMH) and nitrogen tetroxide (NTO) propellants. This paper describes the cryogenic propellant storage design for the TOPS mission and demonstrates how these cryogenic propellants are stored passively for a decade-long Titan mission.

Cryogenic Propellant Storage↗

Long-Term Cryogenic Propellant Storage for the Titan Orbiter Polar Surveyor (TOPS) Mission

Cryogenic propellants such as liquid hydrogen (LH2) and liquid oxygen (LOX) can dramatically enhance NASAs ability to explore the solar system because of their superior specific impulse (Isp) capability. Although these cryogenic propellants can be challenging to manage and store, they allow significant mass advantages over traditional hypergolic propulsion systems and are therefore technically enabling for many planetary science missions. New cryogenic storage techniques such as subcooling and the use of advanced insulation and low thermal conductivity support structures will allow for the long term storage and use of cryogenic propellants for solar system exploration and hence allow NASA to deliver more payloads to targets of interest, launch on smaller and less expensive launch vehicles, or both. Employing cryogenic propellants will allow NASA to perform missions to planetary destinations that would not be possible with the use of traditional hypergolic propellants. These new cryogenic storage technologies were implemented in a design study for the Titan Orbiter Polar Surveyor (TOPS) mission, with LH2 and LOX as propellants, and the resulting spacecraft design was able to achieve a 43 launch mass reduction over a TOPS mission, that utilized a conventional hypergolic propulsion system with mono-methyl hydrazine (MMH) and nitrogen tetroxide (NTO) propellants. This paper describes the cryogenic propellant storage design for the TOPS mission and demonstrates how these cryogenic propellants are stored passively for a decade-long Titan mission.

Cryogenic Propellant Storage↗

Rational design of high-performance low-loading oxygen reduction catalysts for alkaline fuel cells

The lack of mechanistic understanding and catalyst design principles for alkaline electrolytes, especially for the sluggish oxygen reduction reaction, has impeded the advancement of alkaline fuel cells. Here, in this study, we propose a modified volcano plot and apply this rationale to strategically design Pt nanosheets with PdH x nanosheets substrates. This catalyst exhibited high stability with a specific activity of 1.71 mA cm −2 at 0.95 V versus the reversible hydrogen electrode, surpassing the benchmark of Pt/C by 49-fold. Spectroscopic, electrochemical and electron microscopic characterizations revealed that such performance enhancement originated from tensile-strained Pt{111} facets, improving oxidative stability and suppressing carbon corrosion. In fuel cell testing, the catalyst enabled a peak power density of 1.67 W cm −2 with a loading of 10 µg PGM Cathode cm −2 . Further optimization delivered a peak power density of 21.7 W mg −1 PGM Cathode+Anode with a total specific catalyst cost US$\$$1.27 kW −1 , surpassing the US Department of Energy’s Pt group metal loading and cost targets. This study provides valuable insights into catalyst design for the alkaline oxygen reduction reaction.

36 MATERIALS SCIENCE↗

Framework for Coordinated Efforts in the Exploration of Volatiles in the South Polar Region of the Moon

The exploration of the lunar south polar region and the ground truthing of polar volatiles is one of the top priorities for several space agencies and private partners. Here we use Moon Mineralogy Mapper surficial water ice detections to investigate the location of water ice-bearing permanently shaded regions near the south pole. We extract a variety of parameters such as their temperature regime, slope, hydrogen content, number of ice detections, depth stability for water ice and dry ice, and mobility aspects. We identify 169 water ice-bearing PSRs and use their characteristics to identify sites that allow to access the highest abundances of volatiles, sites that can be visited to characterize the lateral or vertical distribution of volatiles (water ice and dry ice), and sites that allow for the fastest recovery of a scientifically interesting sample. Collectively, 37 PSRs are identified as sites of interest, including 11 that would address more than one mission objective and may be, for that reason, higher priority targets of exploration. These PSRs are found in Shoemaker, Faustini, Cabeus, Malapert, Nobile, Sverdrup, Wiechert J and Haworth craters, as well as 3 unnamed craters (PSRs 57, 120, 89). These sites are all located within 6 degrees of the south pole. We present case studies for a relatively short traverse mission (20 to 50 km) to PSR 89, a medium length traverse (~100 km) to Sverdrup 1, and a longer traverse (~300 km) to Cabeus that can serve as a guide in planning upcoming exploration missions.

Myriam Lemelin↗

Orange County Transportation Authority Fuel Cell Electric Bus Progress Report (Feb-Jul 2020) [Slides]

This report presents early results from a deployment of fuel cell electric buses (FCEBs) operated by Orange County Transportation Authority (OCTA) in Southern California. The ten FCEBs, produced by New Flyer, feature an electric drive propulsion system powered by a Ballard fuel cell system. The project team is collaborating with the U.S. Department of Energy (DOE) and DOE's National Renewable Energy Laboratory (NREL) to evaluate the buses in revenue service. The goal of this evaluation is to compare the FCEB performance to that of conventional technology and to track progress over time toward meeting the technical targets set by DOE and the Department of Transportation (DOT). The FCEBs were delivered beginning in late-2019, and were placed in service on February 9, 2020. The data period covers February 2020 through July 2020. NREL collects data on ten 2016 model year compressed natural gas (CNG) buses as a baseline comparison at OCTA.

33 ADVANCED PROPULSION SYSTEMS↗

Leveraging large language models to address data scarcity in machine learning for graphene synthesis

Machine learning in experimental materials science faces significant challenges due to the scarcity of data, which are costly and time-consuming to generate, particularly when relying on in-house experiments. Literature data mining offers a potential solution but introduces issues like mixed data quality, inconsistent formats, and non-uniform reporting of synthesis parameters, resulting in partially missing and heterogeneous features across the dataset. Here, we propose data imputation and feature engineering methods that employ pre-trained large language models (LLMs) to enhance machine learning performance on scarce, heterogeneous datasets, demonstrated on graphene CVD synthesis data and the ML-HydPARK hydrogen storage dataset. GPT models perform data imputation via tailored prompting and semantic normalization of inconsistently reported features through embeddings, for example, to harmonize the complex nomenclature of CVD substrates. Beyond yielding more diverse and richer feature representations than traditional methods such as K-nearest neighbors (KNN) and Multivariate Imputation by Chained Equations (MICE), LLM-based data imputation is evaluated against dataset characteristics and prompting strategies. We vary the level of autonomy granted to the LLM, from generic prompting that leverages pre-trained knowledge for autonomous data generation to data-informed prompting that constrains outputs using target-specific information, and demonstrate which level of autonomy yields superior imputation performance across datasets and feature types. The proposed data engineering methods markedly improve downstream performance; for example, in graphene layer number classification using a support vector machine (SVM), binary accuracy increases from 39% to 65% and ternary accuracy from 52% to 72%. Fine-tuning experiments on both datasets show that combining our proposed LLM-based data imputation and feature encoding methods with numerical machine learning predictors outperforms standalone fine-tuned LLM predictors in data-scarce settings. The proposed strategies emphasize data enhancement techniques rather than refining learning architectures or regularizing loss functions, offering a broadly applicable framework for improving machine learning performance on scarce, inhomogeneous datasets.

Chemical vapor deposition↗

Uncovering hidden market opportunities for advanced nuclear reactors

Decarbonizing to meet aggressive climate change mitigation targets requires energy transition within all sectors. In the industrial sector, global emissions will need to decrease by 65–90% by 2050 to avert warming greater than 1.5°C (Pörtner et al., 2022). Recent U.S. laws, including the Inflation Reduction Act (IRA), Bipartisan Infrastructure Law (BIL), Defense Production Act, Creating Helpful Incentives to Produce Semiconductors (or CHIPS), state programs, and other recent laws, have clean energy requirements and provide financial incentives to accelerate the use of clean energy technologies in the industrial sector. These new laws include supporting mechanisms with direct financial support for nuclear power (e.g., advanced reactor development and hydrogen production). However, advanced nuclear could also gain these financial benefits by coupling with low-carbon industrial projects. For example, microreactors could supply low-carbon energy to producers of critical metals that (1) are eligible to receive investment and production tax credits and favorable loans, and (2) the low-carbon product could gain preference in emerging markets for green products.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Stringer Bending Test Helps Diagnose and Prevent Cracks in the Space Shuttle's External Tank

Space Shuttle Discovery's last mission, STS-133, was scheduled to launch on November 5, 2010. Just hours before liftoff, a hydrogen leak at an umbilical connection scrubbed the launch attempt. After the scrub, further inspection revealed a large crack in the foam insulation covering the External Tank, ET-137. Video replay of the launch attempt confirmed the crack first appeared as cryogenic propellants were being loaded into the ET. When the cracked foam was removed, technicians found the underlying stringer had two 9-inch-long cracks. Further inspection revealed a total of 5 of the 108 ET stringers had cracked. NASA and Lockheed Martin immediately launched an aggressive campaign to understand the cracks and repair the stringers in ET-137, targeting February 2011 as the new launch date for STS-133. Responsibilities for the various aspects of the investigation were widely distributed among NASA centers and organizations. This paper will focus on lab testing at Marshall Space Flight Center (MSFC) in Huntsville, Alabama that was intended to replicate the stringer failure and gauge the effect of proposed countermeasures.

Saxon, Joseph B.↗

Transient Triamidoamine Neptunium(V)–Mono(Imido) Complexes: C–H Activations and Hydrogen Atom Transfer Driven by Effective Nuclear Charge

Metal-mono(imido) linkages have been known for seven decades, and they are found in transition metal, main group, lanthanide, thorium, and uranium complexes. However, transuranium-mono(imido) complexes remain unknown in any scenario. Here, we present evidence for transient neptunium(V)–mono(imido) complexes. Treatment of [Np III (Tren TIPS )] (1, Tren TIPS = {N(CH 2 CH 2 NSiPr i 3 ) 3 } 3– ) with N 3 R (R = SiMe 3 ; 1-adamantyl, Ad) results in N 2 evolution and dark purple solutions consistent with the formation of [Np V (Tren TIPS )(NR)] (3NpNR). However, solutions of 3NpNR rapidly turn orange, where for R = SiMe 3 the isolated 1:1 products are [Np IV (Tren TIPS ){N(H)SiMe 3 }] (4a) and [Np IV (Tren TIPS-2H ){N(H)SiMe 3 }] (4b, Tren TIPS-2H = {N(CH 2 CH 2 NS i Pri 3 ) 2 (NCH 2 CH 2 NSiPr i 2 C[Me]=CH 2 )} 3– ). The latter contains a dehydrogenated-Pr i vinyl functionality accounting for the source of the two amido H atoms. The reaction for R = Ad proceeds similarly, but only [Np IV (Tren TIPS ){N(H)Ad}] (5a) could be unequivocally confirmed, though its isolation suggests generality of the imido-to-amido functional group transformation. Complexes 4a/4b exhibit slow relaxation of their magnetization, adding to the small number of transuranium single ion magnets. Experimental and computational analysis suggests that the amido products are formed by C–H activation and two sequential hydrogen atom transfer reactions involving a three-step proton-coupled electron-transfer sequence of H • radical abstraction, electron transfer, then another H • radical abstraction step. In contrast to transient 3NpNR, the 5f 2 uranium(IV)-imido complex [K(2.2.2-cryptand)][U IV (Tren TIPS )(NSiMe 3 )] (8UNSiMe 3 ) is robust, even in boiling THF, suggesting the transience of 5f 2 3NpNR is not due to the 5f n -count but the increased effective nuclear charge of neptunium vs uranium. This work highlights divergence of uranium- and neptunium-imido stabilities, emphasizing that the latter is an inherently challenging synthetic target.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymorphism of Pb 5 (PO 4 ) 3 OH δ within the LK-99 mixture

During the synthetic exploration targeting the polycrystalline compound LK-99, an unexpected phase, Pb 5 (PO 4 ) 3 OH δ , was identified as a byproduct. We elucidated the composition of this compound through single-crystal X-ray diffraction analysis. Subsequent synthesis of the target compounds was achieved via high-temperature solid-state pellet reactions. The newly identified Pb 5 (PO 4 ) 3 OH δ has an orthorhombic crystal structure with space group Pnma , representing a unique structure differing from the hexagonal apatite phases of Pb 10 (PO 4 ) 6 O and Pb 5 (PO 4 ) 3 OH. Comprehensive temperature- and magnetic-field-dependent magnetization studies unveiled a temperature-independent magnetic characteristic of Pb 5 (PO 4 ) 3 OH δ . Solid-state nuclear magnetic resonance spectroscopy was employed to decipher the origins of the phase stability and confirm the presence of hydrogen atoms in Pb 5 (PO 4 ) 3 OH δ . These investigations revealed the presence of protonated oxygen sites, in addition to the interstitial water molecules within the structure, which may play critical roles in stabilizing the orthorhombic phase.

Xu, Mingyu (ORCID:0000000171386009)↗

Cryogenic Propulsion for the Titan Orbiter Polar Surveyor

Liquid hydrogen (LH2) and liquid oxygen (LO2) cryogenic propellants can dramatically enhance NASA sability to explore the solar system due to their superior specific impulse (Isp) capability. Although these cryogenic propellants can be challenging to manage and store, they allow significant mass advantages over traditional hypergolic propulsion systems and are therefore enabling for many planetary science missions. New cryogenic storage techniques such as sub-cooling and the use of advanced insulation and low thermal conductivity support structures will allow for the long term storage and use of cryogenic propellants for solar system exploration and hence allow NASA to deliver more payloads to targets of interest, launch on smaller and less expensive launch vehicles, or both. These new cryogenic storage technologies were implemented in a design study for the Titan Orbiter Polar Surveyor (TOPS) mission, with LH2 and LO2 as propellants, and the resulting spacecraft design was able to achieve a 43 launch mass reduction over a TOPS mission, that utilized a traditional hypergolic propulsion system with monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants. This paper describes the cryogenic propellant storage design for the TOPS mission and demonstrates how these cryogenic propellants are stored passively for a decade-long Titan mission that requires the cryogenics propellants to be stored for 8.5 years.

Cryogenic Propellant Storage↗

Structure prediction of porous organic crystals

In this work, we explore the possibility of applying automated crystal structure prediction to reproduce the experimentally identified metastable porous polymorphs. Using our recently developed High-Throughput Organic Crystal Structure Prediction ( HTOCSP ) framework, we conducted a systematic study on five representative organic crystalline systems including hydrogen-bonded frameworks (HOFs), featured by the presence of significant porosity, in conjunction with different choices of energy models from classical, machine learning force fields, tight binding to density functional theory. Our results suggest that the current structure generation framework, with careful selection of symmetry conditions, is likely to generate rather complex and abundant metastable crystal candidates for porous crystals. In conjunction with the recent advance in universal machine learning force fields, it becomes possible to identify experimental structures as the energetically favorable candidates from a simple energy versus density analysis, thus paving the way for computational design of complex porous materials with the target systems prior to the experimental synthesis and characterization.

36 MATERIALS SCIENCE↗

Hydrogen Concentrations on C-class Asteroids from Remote Sensing

We present spectroscopic observations of 16 asteroids from 1.9-3.6 microns, collected from the United Kingdom Infrared Telescope (UKIRT) from 1996-2000. Of these 16 asteroids, 11 show some evidence of a 3-micron hydrated mineral absorption feature greater than 2 sigma at 2.9 microns. Using relations first recognized for carbonaceous chondrite powders by Miyamoto and Zolensky (1994) and Sato et al. (1997), we have determined the hydrogen/silicon ratio for these asteroids and calculated their equivalent water contents, assuming all the hydrogen was in water. The asteroids split into two groups, roughly defined as equivalent water contents of greater than approx. 7% (eight asteroids) and less than approx. 3 % (the remaining eight asteroids). This latter group includes some asteroids for which there is a small but statistically significant 3-micron band of non-zero depth. The G-class asteroids in the survey have higher water contents, consistent with CM chondrites. This strengthens the connection between CM chondrites and G asteroids that was proposed by Burbine (1998). We find that the 0.7-micron and 3-micron band depths are correlated for the population of target objects.

Rivkin, A. S.↗

Calcitonin Receptor N-Glycosylation Enhances Peptide Hormone Affinity by Controlling Receptor Dynamics

The class B G protein-coupled receptor (GPCR) calcitonin receptor (CTR) is a drug target for osteoporosis and diabetes. N-glycosylation of asparagine 130 in its extracellular domain (ECD) enhances calcitonin hormone affinity with the proximal GlcNAc residue mediating this effect through an unknown mechanism. Here, we present two crystal structures of salmon calcitonin-bound, GlcNAc-bearing CTR ECD at 1.78 and 2.85 Å resolutions and analyze the mechanism of the glycan effect. The N130 GlcNAc does not contact the hormone. Surprisingly, the structures are nearly identical to a structure of hormone-bound, N-glycan-free ECD, which suggested that the GlcNAc might affect CTR dynamics not observed in the static crystallographic snapshots. Hydrogen-deuterium exchange mass spectrometry and molecular dynamics simulations revealed that glycosylation stabilized a β-sheet adjacent to the N130 GlcNAc and the N-terminal α-helix near the peptide-binding site while increasing flexibility of the peptide-binding site turret loop. These changes due to N-glycosylation increased the ligand on-rate and decreased its off-rate. The glycan effect extended to RAMP-CTR amylin receptor complexes and was also conserved in the related CGRP receptor. These results reveal that N-glycosylation can modulate GPCR function by altering receptor dynamics.

59 BASIC BIOLOGICAL SCIENCES↗