SEARCH · Search NASA
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
High-energy associated with slow absorption-desorption kinetics remains a major challenge of all chemisorption-based CO2 capture technologies, particularly during solvent regeneration. A novel catalytic sorption system, based on aqueous piperidine (C5H10-NH) activated by a deep eutectic solvent (DES), was developed in this research to overcome the challenge.
Direct Reduction of Iron ore using hydrogen (H-DRI) is a promising pathway towards efficient steelmaking and accurate predictive models are a necessity for scale-up and optimization of this technology. However, accurate models of this process remain limited because existing models oversimplify grain-scale phenomena, such as nonlinearity inside grain, self-sufficient porosity, surface reactions, and the role of plasma species. These phenomena are important for flash steelmaking and plasma-assisted H-DRI processes. To address this need, we present a phenomenological model for simulating H-DRI at the scale of a single micron-sized grain of the iron ore. We call this the Transient Reactive Grain Model (TRGM). TRGM incorporates key physical process: gas species transport, a chemical kinetics of material conversion, nanopore structural evolution and, adsorption-desorption surface kinetics at the reactive nanopore surface. The important contribution of this work is that the model provides a dependence on different reductant species, specifically hydrogen atoms versus molecules, so that role of hydrogen plasma reduction can be clarified compared to the use of pure hydrogen gas reduction. TRGM predictions agree well with experimental data for both molecular H2 reduction of Fe2O3 and plasma hydrogen reduction of Fe3O4. Results reveal species concentration gradients with a diffuse reaction zone, and enhanced hydrogen diffusion at the grain outer surface due to evolving porosity. These findings challenge common assumptions in existing models, including sharp reaction fronts, quasi-steady diffusion and kinetics, and the neglect of surface chemistry. As a generalized grain-scale model for H-DRI processes, TRGM has practical applications in flash steelmaking and in-flight reduction using both molecular and plasma hydrogen.
Coastal environments, particularly those adjacent to Superfund sites, are at increased risk of contaminant release during natural disasters, posing serious threats to nearby communities. To investigate this issue, we employed an advanced laboratory flood simulator to impose arsenic-contaminated sediments to turbulent flooding events. We further monitored changes in arsenic collocation and solid-phase speciation using advanced synchrotron radiation-based techniques to understand the impacts of flooding on arsenic mobility. Our results demonstrate that turbulent conditions significantly enhance the resuspension of arsenic-rich sediments, resulting in increased arsenic release into the water. This mobilization is driven by the erosion of the reduced sediments and the redox-mediated transformation and dissolution of Fe and Mn (oxyhydr) oxides, which promote the release of As(III). We found that arsenic speciation on resuspended particles is closely tied to shear stress, with As(V) prevailing at low stress and the more toxic As(III) dominating at higher stress levels. In the post-erosion phase, solid-phase As(III) decreased while dissolved As(III) increased, indicating ongoing desorption. The persistence of multiple arsenic species on resuspended particles marks them as potential long-range transport vectors. Thus, the environmental impact of flooding and sediment resuspension extends beyond the event itself, raising longer-term concerns for arsenic mobility. Our comprehensive geospatial analysis revealed substantial overlap between arsenic-contaminated soils and regions at high risk of flooding and hurricanes across the conterminous United States. This overlap disproportionately impacts economically disadvantaged and marginalized communities. Approximately 40 million Americans reside within 10 kilometers of these high-risk contaminated zones, with nearly 28 million exposed to hurricane threats and around 18 million vulnerable to flooding risks. Alarmingly, over 40% of those affected by hurricanes and 33% of those impacted by flooding belong to underrepresented minority and low-income populations. These findings highlight the urgent need for targeted mitigation strategies to protect public health and address environmental justice concerns.
Integrated CO 2 capture and conversion (ICCC) by hydrogenation is a promising strategy to utilize carbon dioxide and this work add to the effort to elucidate the catalytic hydrogenation mechanism using Ru based dual functional materials (DFM). Ru-Na 2 ZrO 3 DFMs, obtained through different wet methods, were evaluated for the first time and the relationship between Ru and support systematically investigated. The thermally stable and cyclable Ru-Na 2 ZrO 3 -a (obtained without filtration step) exhibited CO 2 conversion of 80% and a higher yield of CO at 400°C compared to previously tested DFM, while the Na depleted/Zr rich Ru-Na 2 ZrO 3 -b resulted in 90% selectivity to CH 4 with yield of 1.11 mmol/g at the same temperature. The in-situ experiments have provided conclusive evidence showing that CO 2 hydrogenation on the two Ru DFMs is fundamentally different. In Ru-Na 2 ZrO 3 -a, the monoclinic Na 2 ZrO 3 support acted as the active centre (not as promoter) for CO 2 bridging binding and hydrogenation to CH 4 at the metal-support interface through associative formate pathway with limited further reduction to methane due to lack of H 2 spillover from the small and well dispersed Ru NPs, which results in CO desorption. Conversely, abundant clusters of larger Ru NPs in Ru-Na 2 ZrO 3 -b, led to CH 4 production due to co-existent Ru on-top direct dissociation of CO 2 (preferential) and monodentate formate adsorption and further methanation. Alkali zirconates doped metals, and their synthesis method could thus play a crucial role in designing tuneable heterogeneous catalysis in C 1 chemistry, which could significantly benefit the environment by lowering CO 2 levels, encouraging cleaner industrial practices, supporting a circular economy, and converting waste CO 2 into valuable products.
The resistance of elastomeric materials to high-pressure hydrogen-induced damage is essential for ensuring the reliability of hydrogen infrastructure. Here, in this study, we systematically investigated the swelling behavior and hydrogen transport properties of four elastomer types – EPDM, NBR, FKM, and HNBR – using a custom in-situ view cell system capable of real-time monitoring during decompression from pressures up to 96.5 MPa. Each elastomer was formulated with and without fillers and plasticizers to assess the effects of formulation on swelling response. Thermal desorption analysis (TDA) was employed to determine equilibrium hydrogen content and diffusion coefficients, providing insight into gas uptake and mobility within each material. Correlation analyses using Pearson and Spearman coefficients revealed that the diffusion coefficient showed a stronger relationship with swelling behavior than hydrogen content, highlighting the dominant role of hydrogen mobility. Filled elastomers, particularly those with carbon black, consistently showed reduced swelling due to enhanced stiffness and reduced diffusivity. These results deepen our understanding of diffuso-mechanical interactions in elastomers and support the rational design of sealing materials for high-pressure hydrogen systems.
As the United States and the global community pursue energy abundance and resilience, hydrogen is becoming a critical energy carrier. The future of hydrogen transport depends on one thing: verifying that today’s pipelines are hydrogen ready. This study investigates the permeation behavior of medium-density polyethylene (MDPE) and high-density polyethylene (HDPE) pipelines under pure hydrogen gas environment at various pressures and temperatures. Using thermal desorption analysis (TDA) and direct pipe permeability measurements, hydrogen loss rates are quantified, revealing minimal permeation losses (< 10.5 g/km/day) under realistic operating conditions. Effects of temperature and pressure with Standard Dimension Ratios (SDR), were evaluated to determine their influence on permeation rates of MDPE and HDPE pipelines. In addition, ex-situ density and degree of crystallinity (DOC) of MDPE and HDPEs after hydrogen exposure were also investigated to understand pressure-dependency of polymer properties. The findings provide essential data for assessing polymer-based pipeline materials for safe and reliable hydrogen transport.
Modeling hydrogen evolution reaction (HER) activity probability on IrPdPtRhRu(1 1 1) high-entropy alloys. Determining hydrogen coverages based on ligand effects and generalized hydrogen–hydrogen repulsion. The rate of H 2 formation is highly impacted by the level of hydrogen coverage on the catalyst surface. In search of optimal catalytic properties high-entropy alloys (HEA) are promising candidates that utilize the compositional space of multiple elements. Based on simulations of HEA model (1 1 1) surfaces with a range of hydrogen coverages, distributions of binding energies are used to construct a framework that approximates the probability that adsorbed hydrogen may lead to the formation of H 2 as a function of applied potential. By optimizing the alloy compositions for the highest activity probability at given potentials the best and most efficient catalyst candidates for HER can be identified. Treating hydrogen–hydrogen repulsion effects and binding energy separately, we find that the repulsion is larger for HEAs than for pure metals. Differing isotherm slopes in the mean adsorption and desorption energies demonstrate a possible hysteresis for hydrogen adsorption on HEAs.
Here, the activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H 2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu 2 O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu 2 O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H 2 pressures reveal that Rh significantly accelerates the reduction of these Cu 2 O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu 2 O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu 2 O is active for H 2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H 2 on thin-film Cu 2 O with Rh underneath is the adsorption of H 2 on the buried Rh site, and once adsorbed, the dissociation of H 2 is barrierless. These calculations also explain why H 2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.
Aluminosilicate materials have been extensively studied as efficient aldol catalysts for C-C coupling reactions due to their acidic nature, high surface area, thermal stability, and porous structure. This work investigated the impact of water vapor pressure on the catalytic reactivity of aluminosilicates for the aldol condensation of propanal to 2-methyl-2-pentenal (MP). The catalytic performance of amorphous SiO2-Al2O3 (A-Si-Al) and aluminated MCM-41 (Al-MCM-41) for the vapor-phase aldol condensation of propanal was evaluated at 200 degrees C as a function of vapor-phase water content at atmospheric pressure. Our findings demonstrate that co-feeding low water vapor pressures (1-18 kPa) with propanal enhances the rates of MP production at 200 degrees C on A-Si-Al. Conversely, water vapor pressures of 25 kPa result in a decrease in aldol dimer formation rates. The rate of MP production evaluated on Al-MCM-41 also increased in the presence of 5 kPa water compared to anhydrous conditions. Propylamine temperature-programmed desorption analyses revealed an increase in Bronsted acid site density when both catalysts were exposed to water, which likely accounts for the observed enhancement in aldol condensation reactivity under hydrous conditions. Reversibility testing of the water vapor effect under reaction conditions, combined with X-ray diffraction analysis of fresh, spent, and regenerated catalysts, revealed no structural changes in either aluminosilicate upon exposure to water or reaction conditions. The rates of aldol condensation and the impact of water vapor were highly consistent across both materials, suggesting that zeolite crystallinity has minimal influence on the catalytic performance.
Microbial life on plastic debris, called plastisphere, has invoked special attention on aquatic ecosystems as emerging habitats for antibiotic resistance genes (ARGs) and antibiotic-resistant bacteria (ARB). There is scarce information concerning how properties of plastics influence ARGs and ARB, the effect of biofilms on enrichment of ARGs and ARB, and, especially, the influence of plastic transformation on ARGs and ARB. Limited research has shown that microplastic (MP) surfaces influence proliferation of antibiotic resistance (AR), aged MPs exhibit increased toxicity due to more adsorption-desorption of AR, and MP transformation is correlated with disseminating AR. Prevention measures of AR include minimizing MP releasing into aquatic environments and sewage treatment plants. The future research should aim to identify the interface mechanisms of transformed MNPs and antibiotics alone, or mixed with other contaminants, property changes of MNPs, and associated toxicity evaluation.
There are limited studies of functionalized silica anion exchange sorbents used for critical/heavy metal recovery/removal relative to polymeric and other inorganic materials. This work features ammonium-coordinated exchanger (ACE) anion exchange particle sorbents prepared by either acid-washing epoxy-crosslinked polyethylenimine (PEI) hydrogen bonded within/to a silica particle sorbent (two-step method) or reacting a di-chlorinated crosslinker, α,α-dichloro-p-xylene (DPX), with PEI within silica (single-step method). Energy dispersive X-ray spectroscopy (EDS) and infrared spectroscopy confirmed the presence of -NH 2 + ···Cl - and -NH 3 + ···Cl - groups, which removed oxyanionic species –arsenate, selenate, chromate, sulfate, phosphate, and nitrate– plus bromide from ideal solutions, authentic acid mine drainage (AMD), and authentic flue gas desulfurization (FGD) wastewater. Affinity of the anions for ACE varied across single- and mixed-element solutions. However, affinity for CrO 4 2- was among the highest in both cases. Total anion uptake by the optimized ACE, PEI-E3-HCl_1.1, reached 1.2 mmol anion/g-sorb. (0.56 mmol CrO 4 2- /g), or ∼2.3 mmol negative charge/g-sorb. This was close to the 0.52 mmol CrO 4 2- /g of a commercial anion exchange resin. Near-consistent removal of 20–80 % of each anion from FGD during an eight-cycle adsorption-desorption (1 M NaCl) test predicted good ACE viability for testing under practical conditions at larger scale.
A high potential cost-effective and environmentally friendly method has been applied for recycling anisotropic Nd-Fe-B bonded magnets. Waste additively printed Hydrogenation-Disproportionation-Desorption-Recombination (HDDR) Nd-Fe-B anisotropic bonded magnet was pulverized into composite powder containing Nd-Fe-B particles and nylon binder through cryomilling at a liquid nitrogen temperature (~77 K) under Ar inert atmosphere. Then, the cryomilled composite powder was warm compacted into a bonded magnet. Further, the magnetic particles were aligned during post-compaction annealing under a magnetic field of 30 kOe. The recycled bonded magnets have a higher density (3% enhancement), but slightly inferior magnetic properties compared to the original magnets, i.e., the magnetic remanence, coercivity and maximum energy product are reduced by 2%, 3% and 8%, respectively. The scanning electron microscopy revealed that some HDDR Nd-Fe-B powder crumbled into fine particles during cryomilling. Powder X-ray diffraction showed a small amount of Nd-oxide impurity in the cryomilled powder. The slightly deteriorated magnetic properties are ascribed to the oxidation of Nd-Fe-B particles due to formation of fresh fracture surface during cryomilling. The approach enables the direct reuse of end-of-life bonded magnets in an economical and environmentally friendly way.
The impact of the neutron-displacement damage on phase stability and microstructure of substoichiometric yttrium dihydrides (YH x , x <2) were investigated to assess their use as solid moderator in high-temperature nuclear reactors. YH x specimens were, thus, subjected to neutron irradiations in the range of 0.1–2 displacements per yttrium atom (dpa-Y) in the temperature range of 536–878°C at the Oak Ridge National Laboratory's (ORNL's) High Flux Isotope Reactor (HFIR). YH x specimens were initially prepared at stoichiometry (H/Y) ratios of 1.69 and 1.83. HFIR-irradiated specimens were characterized by variety of techniques to investigate H retention characteristics including dimensional analysis, optical microscopy, scanning electron microscopy electron back scatter diffraction (EBSD), transmission electron microscopy, thermal desorption spectroscopy (TDS), and high-energy x-ray diffraction (HE-XRD) characterizations. Overall, YH x exhibited notable structural and phase stability under short-term neutron-irradiation, except for the samples with significant silicon carbide (SiC) interaction at high doses and temperatures. Basic dimensional and mass measurements were misleading for accurate assessment of H retention, as confirmed by EBSD phase maps, XRD line profiles, and TDS signals. Thus, it was discussed that a robust H retention metric is needed to assess irradiated hydrides. Further, nanoscale cavities were observed as a result of the neutron irradiation in all samples. Although no clear impact of dose and irradiation temperature was determined, the initial H/Y ratio had an impact on the cavity number density where low H/Y specimens had high-resistance to cavity formation. The Y-vacancy cluster formation at the collision stage of the displacement cascade and their stabilization by H were considered to be the likely underlying mechanisms for the observed cavity microstructure.
The effect of mixed spectra and thermal neutron shielded irradiation on tungsten was evaluated with plasma exposure in the tritium plasma experiment followed by thermal desorption spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The two different irradiation campaigns were performed at the High Flux Isotope Reactor to 0.39–0.74 displacement per atom (dpa) in the 894–1379 K temperature range. A neutron spectrum influence on the void size and void number density was not observed. However, a strong correlation was found between void size and void number density with temperature, but not with dpa in the limited dpa range of this study. Thermal neutron shielding significantly reduced the transmutation to Re+Os. Higher irradiation temperature will lead to larger voids with lower number density, which reduces deuterium retention. In conclusion, grain growth was also observed for high-temperature irradiation of over ~1300 K within the limited grains visible in the transmission electron microscopy specimens.
Deuterium supersaturated surface layer (DSSL) in tungsten, a few nm thick layer exhibiting extremely high deuterium content (> 5%), has been studied as a function of deuterium plasma ion flux and fluence. Tungsten samples were exposed at 400 K and deuterium ion energy of ∼ 60 eV. The deuterium ion flux spanned over an order of magnitude, being 7.3 × 10 20 , 4.2 × 10 21 , and 3.8 × 10 22 D/m 2 . The fluence ranged from 3.4 × 1024 to 3.4 × 1025 D/m2. The samples and their deuterium content were analyzed by nuclear reaction analysis (NRA), scanning transmission electron microscopy (STEM), and thermal desorption spectroscopy (TDS). The largest thickness of DSSL was found to be around 10.5 nm and was observed in the case of the highest exposure flux and fluence, whereas the layer was only about 3.8 nm thick in the case of the lowest value of the two parameters. The thickness of the DSSL was found to monotonically increase with both deuterium flux and fluence. Finally, similar to the thickness, the estimated D concentration seems to follow the same trend, increasing from the lowest value of around 3 at.% to the highest value of around 5 at.%.
Fuel retention in dust accumulated in fusion devices is a potential operational hazard. Boronization is one of the leading wall-conditioning candidates for future fusion devices. Fuel retention characteristics of boron dust must be studied to accurately understand the potential hazards of boron dust in fusion devices. We evaluated the retention of deuterium (D) in commercially available boron powder as a proxy for tritium retention in boron dust. Diffuse reflectance infrared Fourier transform spectroscopy revealed that boron powder between 300 and 500 K exposed to neutral hydrogen (H 2 ) gas retains H via B-H bonding. We utilized D 2 exposures of 17,400 L on the boron powder, which led to retention on the order of 0.5 g D per 100 kg B or 1.2 g D per m 2 B, as estimated from temperature programmed desorption measurements. We evaluated how powder bakeouts under ultra-high vacuum (UHV), or in an oxygen (O 2 ) or H 2 gas backfilled environment can remove the retained fuel. Bakeouts below 523 K under UHV exhibited poor D removal, promoting recapture of D 2 present as background gas in the chamber. Higher temperature bakeouts led to the removal of over 80% of the retained D within 3 days (623 K) or 1 h (723 K). Bakeouts at 423 K under an O 2 gas environment removed ∼150% more retained D from the boron powder, when compared to bakeouts conducted under UHV. These results suggest that efficient fuel removal from boron dust can be achieved by high-temperature bakeout (>623 K) or by bakeouts at lower temperature (423 K) under an O 2 environment.
Hydrides that retain their hydrogen in service are critical for advanced microreactor and space nuclear systems. Hydrogen retention is affected by evolving microstructure under temperature and irradiation extremes. This study investigated microstructural features in neutron-irradiated yttrium hydride and the stability of these features under thermal cycles. Differential scanning calorimetry was used to determine hydrogen desorption and temperatures at which significant phase changes are occurring, and transmission electron microscopy was used for microstructural analysis after each thermal cycle. Cyclic heating led to crystallization and epitaxial growth of surface oxidation and dehydriding of the matrix. Other features such as the bulk matrix crystal structure, irradiation-induced cavities, and matrix precipitation remained constant after thermal cycling. Results allow us to design better hydride alloys through microstructure tailoring and potential irradiation conditioning treatments.
This work is focused on advancing of the understanding the carbon dioxide (CO2) sorption characteristics of imidazolium ionic liquid crystals based on the 1-alkyl-3-methylimidazolium (Cnmim) ionic liquid family. Specifically, the mechanism of sorption across the melting, liquid crystal, and isotropic liquid transitions is investigated for 1-tetradecyl-3-methylimidazolium tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-). A unique reversible CO2 occlusion was observed in 1-tetradecyl-3-methylimidazolium tetrafluoroborate (C14mim BF4) under rapid temperature quench from the liquid phases to the solid phase, while complete desorption occurred upon heating above the melting point (40 degrees C). In situ wide-angle x-ray scattering revealed that the lamellar structure of C14mim BF4 liquid crystal phases provides a high concentration of dynamically accessible anion and cation interaction sites for CO2, facilitating CO2 occlusion upon rapid solidification. The selective occlusion of CO2 in C14mim BF4 suggests a new mechanism for CO2 sorption processes.