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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

High Layer Uniformity of Two-Dimensional Materials Demonstrated Surprisingly from Broad Features in Surface Electron Diffraction

Paradoxically, a very broad diffraction background, named the bell-shaped-component (BSC), has been established as a feature of graphene growth. Recent diffraction studies as a function of electron energy have shown that the BSC is not related to scattering interference. Here, additional experiments are carried out as a function of temperature over the range in which single-layer graphene (SLG) grows. Quantitative fitting of the profiles shows that the BSC follows the increase of the Gr(10) spot, proving directly that the BSC indicates high-quality graphene. Additional metal deposition experiments provide more information about the BSC. The BSC is insensitive to metal deposition, and it increases with metal intercalation, because a more uniform interface forms between graphene and SiC. These experiments support the conclusion that the BSC originates from electron confinement within SLG, and surprisingly, it is an excellent measure of graphene uniformity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nanoconfinement of Carbon Dioxide within Interfacial Aqueous/Ionic Liquid Systems

Nanoporous, gas-selective membranes have shown encouraging results for the removal of CO 2 from flue gas, yet the optimal design for such membranes is often unknown. Therefore, we used molecular dynamics simulations to elucidate the behavior of CO 2 within aqueous and ionic liquid (IL) systems ([EMIM][TFSI] and [OMIM][TFSI]), both confined individually and as an interfacial aqueous/IL system. We found that within aqueous systems the mobility of CO 2 is reduced due to interactions between the CO 2 oxygens and hydroxyl groups on the pore surface. Within the IL systems, we found that confinement has a greater effect on the [EMIM][TFSI] system as opposed to the [OMIM][TFSI] system. Paradoxically, the larger and more asymmetrical [OMIM]+ molecule undergoes less efficient packing, resulting in fewer confinement effects. Finally, free energy surfaces of the nanoconfined aqueous/IL interface demonstrate that CO 2 will transfer spontaneously from the aqueous to the IL phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Statistical Analysis of Intertube Tunneling Contacts in the Macroscopic Electrical Conductivity of Carbon Nanotube Fibers

Here, this study investigates the influence of tunneling contact resistances between carbon nanotubes (CNTs) on electron transport and electrical conductivity of macroscopic carbon nanofibers (CNFs), which profoundly impacts the performance of CNT thin film electronics, CNF electron emitters and cathodes, and energy conversion and storage devices. Utilizing a self-consistent electrical contact model coupling a transmission line model with tunneling current, we calculate the contact resistances of a plethora of CNT-CNT contacts within a CNF fiber, which consists of aligned, densely packed CNTs. A statistical analysis is conducted, using Gaussian distributions to account for variations in contact lengths, tunneling gap distances, and single CNT aspect ratios, to calculate the CNT-CNT contact resistance and the overall resistance of CNT fiber. By scaling our model to a macroscopic level, our results are in good agreement with experimental measurements. Our calculation suggests that while increasing the contact overlap length diminishes individual CNT-CNT contact resistance, it could paradoxically increase macroscopic CNT fiber resistance for a given constant CNF mass density, which is due to that fact that a larger overlap length allows more CNTs to pack along an electrical conduction path per unit length, leading to more tunneling contact junctions connected in series and thus less number of parallel conduction paths within the fiber cross section. Increasing tunneling gap distance increases both individual contact and overall fiber resistance. This research provides a simple design tool for tailoring CNT fiber electrical properties to promote real-world applications using CNTs or similar low-dimensional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Boiling Transitions During Droplet Contact on Superheated Nano/Micro-Structured Surfaces

Manipulating surface topography is one of the most promising strategies for increasing the efficiency of numerous industrial processes involving droplet contact with superheated surfaces. In such scenarios, the droplets may immediately boil upon contact, splash and boil, or could levitate on their own vapor in the Leidenfrost state. In this work we report the outcomes of water droplets coming in gentle contact with designed nano/micro-textured surfaces at a wide range of temperatures as observed using high-speed optical and X-ray imaging. Further, we report a paradoxical increase in the Leidenfrost temperature ($T_{\text{LFP}}$) as the texture spacing is reduced below a critical value (~10 μm) that represents a minima in $T_{\text{LFP}}$. Although droplets on such textured solids appear to boil upon contact, our studies suggest that their behavior is dominated by hydrodynamic instabilities implying that the increase in $T_{\text{LFP}}$ may not necessarily lead to enhanced heat transfer. On such surfaces, the droplets display a new regime characterized by splashing accompanied by a vapor jet penetrating through the droplets before they transition to the Leidenfrost state. We provide a comprehensive map of boiling behavior of droplets over a wide range of texture spacings that may have significant implications towards applications such as electronics cooling, spray cooling, nuclear reactor safety and containment of fire calamities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Chlorophyllase from Arabidopsis thaliana Reveals an Emerging Model for Controlling Chlorophyll Hydrolysis

Chlorophyll (Chl) is one of Nature’s most complex pigments to biosynthesize and derivatize. This pigment is vital for survival and also paradoxically toxic if overproduced or released from a protective protein scaffold. Therefore, along with the mass production of Chl, organisms also invest in mechanisms to control its degradation and recycling. One important enzyme that is involved in these latter processes is chlorophyllase. This enzyme is employed by numerous photosynthetic organisms to hydrolyze the phytol tail of Chl. Although traditionally thought to catalyze the first step of Chl degradation, recent work suggests that chlorophyllase is instead employed during times of abiotic stress or conditions that produce reactive oxygen species. However, the molecular details regarding how chlorophyllases are regulated to function under such conditions remain enigmatic. Here, we investigate the Arabidopsis thaliana chlorophyllase isoform AtCLH2 using site-directed mutagenesis, mass spectrometry, dynamic light scattering, size-exclusion multiangle light scattering, and both steady-state enzyme kinetic and thermal stability measurements. Through these experiments, we show that AtCLH2 exists as a monomer in solution and contains two disulfide bonds. One disulfide bond putatively maps to the active site, whereas the other links two N-terminal Cys residues together. These disulfide bonds are cleaved by chemical or chemical and protein-based reductants, respectively, and are integral to maintaining the activity, stability, and substrate scope of the enzyme. This work suggests that Cys residue oxidation in chlorophyllases is an emerging regulatory strategy for controlling the hydrolysis of Chl pigments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Edge States Drive Exciton Dissociation in Ruddlesden–Popper Lead Halide Perovskite Thin Films

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemical stability relative to those fabricated from 3D phases. However, reports of efficient charge separation and current collection are in apparent contradiction with the well-known enhancement of the exciton binding energy in multilayered halide perovskites, which should lower the device’s internal quantum efficiency and voltage. This controversy has led to various proposals for the electronic and physical structure of RPP thin films, including phase inhomogeneity as the driving force for exciton dissociation and transport. We address this apparent paradox in high-quality hot-cast RPP films by correlating ultrafast transient absorption spectroscopy with X-ray scattering measurements. We show that a hot-casting fabrication method produces highly phase pure n = 3 (BA) 2 (MA) n-1 Pb n I 3n+1 RPP structures. The high-phase purity and large grain sizes allow us to observe vertical transport of excitons via a diffusive process and allow us to determine that charge separation is primarily driven by dissociation at surface localized subgap electronic states. Furthermore, we analyze the differential absorption kinetics in films of varying thickness to directly determine that the excitonic diffusion constant is ~0.18 cm 2 s –1 . We propose that a surface localized structural distortion, observed using surface selective grazing incidence X-ray scattering measurements, is responsible for the creation of the surface localized defect states. We find that the density and spatial distribution of these defect states is a function of preparation conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Resonant Multiple-Phonon Absorption Causes Efficient Anti-Stokes Photoluminescence in CsPbBr 3 Nanocrystals

Lead halide perovskite nanocrystals, such as CsPbBr 3 , exhibit efficient photoluminescence (PL) up-conversion, also referred to as anti-Stokes photoluminescence (ASPL). This is a phenomenon where irradiating nanocrystals up to 100 meV below gap results in higher energy band edge emission. Most surprising is that ASPL efficiencies approach unity and involve single-photon interactions with multiple phonons. This is unexpected given the statistically disfavored nature of multiple-phonon absorption. Here, in this study, we report and rationalize near-unity anti-Stokes photoluminescence efficiencies in CsPbBr 3 nanocrystals and attribute them to resonant multiple-phonon absorption by polarons. The theory explains paradoxically large efficiencies for intrinsically disfavored, multiple-phonon-assisted ASPL in nanocrystals. Moreover, the developed microscopic mechanism has immediate and important implications for applications of ASPL toward condensed phase optical refrigeration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Chemical Redox Agent-Driven Noncorrosive Formation of Nanoporous Mg Structures for Advanced Hydrogen Storage

Light metal-based nanomaterials are widely used for energy storage due to their high energy density and surface-to-volume ratio. However, their high reactivity is paradoxically both the source of advantageous properties and a hurdle to the fabrication of stable nanostructures. Here, in this study, we demonstrate the formation of nanoporous Mg via chemical redox agent-driven dealloying, which ensures minimized surface passivation and results in fine nanostructures with <50 nm of interconnected metallic ligament despite the labile chemical properties of Mg. The thin passivation layer protects the metallic ligaments from severe coarsening by suppressing surface diffusion. The hydrogen storage performance of nanoporous Mg is investigated as an exemplar for energy applications, and the hydrogen ab/desorption kinetics is substantially enhanced compared to other nano-Mg with similar dimensions. Mesoscale simulations highlight the significance of the bicontinuous structure compared to the particle-like counterpart. This work offers valuable insights into the unexplored realm of reactive metal-based nanoporous structures, highlighting their potential for sustainable energy storage and carrier media.

08 HYDROGEN↗
DOE OSTI2020

Toward Long-Term Accurate and Continuous Monitoring of Nitrate in Wastewater Using Poly(tetrafluoroethylene) (PTFE)–Solid-State Ion-Selective Electrodes (S-ISEs)

Long-term accurate and continuous monitoring of nitrate (NO 3 – ) concentration in wastewater and groundwater is critical for determining treatment efficiency and tracking contaminant transport. Current nitrate monitoring technologies, including colorimetric, chromatographic, biometric, and electrochemical sensors, are not feasible for continuous monitoring. In this work, we addressed this challenge by modifying NO 3 – solid-state ion-selective electrodes (S-ISEs) with poly(tetrafluoroethylene) (PTFE, (C 2 F 4 ) n ). The PTFE-loaded S-ISE membrane polymer matrix reduces water layer formation between the membrane and electrode/solid contact, while paradoxically, the even more hydrophobic PTFE-loaded S-ISE membrane prevents bacterial attachment despite the opposite approach of hydrophilic modifications in other antifouling sensor designs. Specifically, an optimal ratio of 5% PTFE in the S-ISE polymer matrix was determined by a series of characterization tests in real wastewater. Five percent of PTFE alleviated biofouling to the sensor surface by enhancing the negative charge (–4.5 to –45.8 mV) and lowering surface roughness (Ra: 0.56 ± 0.02 nm). It simultaneously mitigated water layer formation between the membrane and electrode by increasing hydrophobicity (contact angle: 104°) and membrane adhesion and thus minimized the reading (mV) drift in the baseline sensitivity (“data drifting”). Long-term accuracy and durability of 5% PTFE-loaded NO 3 – S-ISEs were well demonstrated in real wastewater over 20 days, an improvement over commercial sensor longevity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

High Resolution Infrared Spectroscopy of Highly Reactive Chemical Intermediates: Berkeley Inspiration and a C.B. Moore Retrospective

One of the long-standing paradoxes in chemistry is that the molecular species of greatest interest are often highly reactive chemical intermediates and thus present only at vanishingly small concentrations under typical steady state conditions. Here, this has proven both a key frustration and powerful motivation for physical chemists in probing such species, particularly for high resolution laser spectroscopic methods in the infrared. Over the past 4-5 decades, this fundamental sensitivity challenge has stimulated the development of many novel techniques for efficient generation, cooling, and infrared probing of such transient chemical intermediates, achieving increasingly sophisticated levels of spectroscopic detail, chemical insight, and a testbed for comparison with first principles ab initio quantum calculations. Two of the pioneering contributors to this scientific arena have been George Pimentel and C. Bradley Moore, both responsible for nourishing DJN’s own enduring fascination with spectroscopic IR study of elusive chemical intermediates. This chapter is not intended to provide a comprehensive review of this large and enormously successful field, but it rather more simply attempts to capture a few selective “Moore-centric” snapshots of the Nesbitt group scientific evolution, specifically in i) advances by Pimentel for the original development of rapid scan flash kinetic spectroscopy based on spectrometers with rapidly rotating IR gratings, ii) the modernization/extension of these methods in the Moore group toward the first high resolution IR laser spectroscopy of singlet/triplet methylene 1,3 CH 2 diradical, and finally to iii) the development of slit supersonic discharge expansion methods at JILA for sub-Doppler infrared laser study of multiple radicals, jet cooled molecular ions, and highly reactive chemical intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Bulky Phosphine Ligands Promote Palladium-Catalyzed Protodeboronation

The Suzuki-Miyaura cross-coupling reaction is plagued by protodeboronation, an undesirable side reaction with water that consumes the boronic acid derivatives required for the cross-coupling reaction. Meticulous mechanistic studies have previously established protodeboronation to be highly sensitive to the nature of the boronic reagent and reaction conditions. Particularly, the presence of bases, which are essential for the Suzuki-Miyaura coupling, is known to catalyze protodeboronation. However, protodeboronation catalyzed by palladium-phosphine complexes, the benchmark catalyst system for Suzuki-Miyaura cross-coupling, has been understudied compared to its base-catalyzed counterpart. Here, we demonstrate, using automated high-throughput experimentation, comprehensive computational mechanistic analyses and kinetic modeling, that protodeboronation is accelerated by palladium(II) complexes bound to bulky phosphine ligands. While sterically hindered ligands are typically used to facilitate difficult cross-couplings, these ligands can instead paradoxically impede cross-coupling product formation, requiring careful and judicious consideration when choosing ligands for Suzuki-Miyaura cross-couplings.

Ser, Cher Tian [University of Toronto, ON (Canada)↗
DOE OSTI2021

Methane Plume Emissions Associated With Puget Sound Faults in the Cascadia Forearc

Methane gas plumes have been discovered to issue from the seafloor in the Puget Sound estuary. These gas emission sites are co-located over traces of three major fault zones that fracture the entire forearc crust of the Cascadia Subduction Zone. Multibeam and single-beam sonar data from cruises conducted in 2011, 2018, 2019, 2020 and 2021 identified the acoustic signature of over 330 bubble plumes. Dissolved gas from the plumes combines to elevate seawater methane concentrations of the entire Puget Sound estuary. Fluid samples from adjacent terrestrial hot springs and deep-water wells surrounding the estuary contain a helium-3 isotope signature, indicating a deep fluid source located near the underlying Cascadia Subduction Zone. However, Puget Sound seawater emission sites lack chemical isotope signatures and elevated thermal anomalies expected from association with a deep plate-interface reservoir. The existence of vigorous marine methane plumes located in areas of thin sediment cover and above the traces of deeply-penetrating forearc fault zones – but still presenting no thermal or chemical anomalies that are found in many other similar forearc environments and remain an unresolved paradox.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

On the Morphodynamics of a Wide Class of Large‐Scale Meandering Rivers: Insights Gained by Coupling LES With Sediment‐Dynamics

Abstract In meandering rivers, interactions between flow, sediment transport, and bed topography affect diverse processes, including bedform development and channel migration. Predicting how these interactions affect the spatial patterns and magnitudes of bed deformation in meandering rivers is essential for various river engineering and geoscience problems. Computational fluid dynamics simulations can predict river morphodynamics at fine temporal and spatial scales but have traditionally been challenged by the large scale of natural rivers. We conducted coupled large‐eddy simulation and bed morphodynamics simulations to create a unique database of hydro‐morphodynamic data sets for 42 meandering rivers with a variety of planform shapes and large‐scale geometrical features that mimic natural meanders. For each simulated river, the database includes (a) bed morphology, (b) three‐dimensional mean velocity field, and (c) bed shear stress distribution under bankfull flow conditions. The calculated morphodynamics results at dynamic equilibrium revealed the formation of scour and deposition patterns near the outer and inner banks, respectively, while the location of point bars and scour regions around the apexes of the meander bends is found to vary as a function of the radius of curvature of the bends to the width ratio. A new mechanism is proposed that explains this seemingly paradoxical finding. The high‐fidelity simulation results generated in this work provide researchers and scientists with a rich numerical database for morphodynamics and bed shear stress distributions in large‐scale meandering rivers to enable systematic investigation of the underlying phenomena and support a range of river engineering applications.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Fracture Intensity Impacts on Reaction Front Propagation and Mineral Weathering in Three‐Dimensional Fractured Media

Abstract Studying reaction front propagation in heterogeneous natural settings is challenging, but numerical simulations can provide insight into the varying spatial and temporal scales of reaction front propagation. Here, the impact of increasing fracture intensity on mineral dissolution rates, and the extent of reaction front propagation is investigated using reactive transport simulations in upscaled discrete fracture network domains with varied fracture intensity. Domain‐averaged dissolution rates vary less than 0.5 log units regardless of the fracture intensity, but the spatial distribution of reactions is controlled by the location and number of dead‐end fractures and the number of connected flowpaths through the domain. Higher fracture intensities lead to more weathering in the domain because of more available mineral for water‐rock interactions. We find that reaction fronts propagate through the primary flowpaths in the first 10,000 years of the simulation for a 10‐m length domain, then propagate into secondary flowpaths and dead‐end fractures between 10,000 and 100,000 years, and finally into the matrix over timescales of hundreds of thousands of years. The domain‐averaged reaction rates decrease through time corresponding to a transition from dissolution in advection‐dominated, fast‐flowing pathways, to dissolution in transport‐limited zones of disconnected fractures and matrix. Matrix dissolution, or dissolution under transport‐limited conditions, is the dominant process at late times in these simulations. The results of these simulations recreate the observed paradox found in nature where highly fractured hillslopes tend to be more weathered but have slower weathering rates, while hillslopes with fewer fractures, are less weathered but have higher dissolution rates.

58 GEOSCIENCES↗
DOE OSTI2022

Resolving the structure of phage–bacteria interactions in the context of natural diversity

Microbial communities are shaped by viral predators. Yet, resolving which viruses (phages) and bacteria are interacting is a major challenge in the context of natural levels of microbial diversity. Thus, fundamental features of how phage-bacteria interactions are structured and evolve in the wild remain poorly resolved. Here we use large-scale isolation of environmental marine Vibrio bacteria and their phages to obtain estimates of strain-level phage predator loads, and use all-by-all host range assays to discover how phage and host genomic diversity shape interactions. We show that lytic interactions in environmental interaction networks (as observed in agar overlay) are sparse—with phage predator loads being low for most bacterial strains, and phages being host-strain-specific. Paradoxically, we also find that although overlap in killing is generally rare between tailed phages, recombination is common. Together, these results suggest that recombination during cryptic co-infections is an important mode of phage evolution in microbial communities. In the development of phages for bioengineering and therapeutics it is important to consider that nucleic acids of introduced phages may spread into local phage populations through recombination, and that the likelihood of transfer is not predictable based on lytic host range.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Comparison of temperature and doping dependence of elastoresistivity near a putative nematic quantum critical point

Abstract Strong electronic nematic fluctuations have been discovered near optimal doping for several families of Fe-based superconductors, motivating the search for a possible link between these fluctuations, nematic quantum criticality, and high temperature superconductivity. Here we probe a key prediction of quantum criticality, namely power-law dependence of the associated nematic susceptibility as a function of composition and temperature approaching the compositionally tuned putative quantum critical point. To probe the ‘bare’ quantum critical point requires suppression of the superconducting state, which we achieve by using large magnetic fields, up to 45 T, while performing elastoresistivity measurements to follow the nematic susceptibility. We performed these measurements for the prototypical electron-doped pnictide, Ba(Fe 1− x Co x ) 2 As 2 , over a dense comb of dopings. We find that close to the putative quantum critical point, the elastoresistivity appears to obey power-law behavior as a function of composition over almost a decade of variation in composition. Paradoxically, however, we also find that the temperature dependence for compositions close to the critical value cannot be described by a single power law.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Multiple sources of aerobic methane production in aquatic ecosystems include bacterial photosynthesis

Aquatic ecosystems are globally significant sources of the greenhouse gas methane to the atmosphere. Until recently, methane production was thought to be a strictly anaerobic process confined primarily to anoxic sediments. However, supersaturation of methane in oxygenated waters has been consistently observed in lakes and the ocean (termed the ‘methane paradox’), indicating that methane can be produced under oxic conditions through unclear mechanisms. Here we show aerobic methane production from multiple sources in freshwater incubation experiments under different treatments and based on biogeochemical, metagenomic, and metatranscriptomic data. We find that aerobic methane production appears to be associated with (bacterio)chlorophyll metabolism and photosynthesis, as well as with Proteobacterial degradation of methylphosphonate. Genes encoding pathways for putative photosynthetic- and methylphosphonate-based methane production also co-occur in Proteobacterial metagenome-assembled genomes. Our findings provide insight into known mechanisms of aerobic methane production, and suggest a potential co-occurring mechanism associated with bacterial photosynthesis in aquatic ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Structural basis for botulinum neurotoxin E recognition of synaptic vesicle protein 2

Botulinum neurotoxin E (BoNT/E) is one of the major causes of human botulism and paradoxically also a promising therapeutic agent. Here we determined the co-crystal structures of the receptor-binding domain of BoNT/E (H C E) in complex with its neuronal receptor synaptic vesicle glycoprotein 2A (SV2A) and a nanobody that serves as a ganglioside surrogate. These structures reveal that the protein-protein interactions between H C E and SV2 provide the crucial location and specificity information for H C E to recognize SV2A and SV2B, but not the closely related SV2C. At the same time, H C E exploits a separated sialic acid-binding pocket to mediate recognition of an N-glycan of SV2. Structure-based mutagenesis and functional studies demonstrate that both the protein-protein and protein-glycan associations are essential for SV2A-mediated cell entry of BoNT/E and for its potent neurotoxicity. Our studies establish the structural basis to understand the receptor-specificity of BoNT/E and to engineer BoNT/E variants for new clinical applications.

59 BASIC BIOLOGICAL SCIENCES↗