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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Spatial mapping of plant N-glycosylation cellular heterogeneity inside soybean root nodules provided insights into legume-rhizobia symbiosis

Although ubiquitously present, information on the function of complex N-glycan posttranslational modification in plants is very limited and it is often neglected. In this work, we adopted an enzyme-assisted matrix-assisted laser desorption/ionization mass spectrometry imaging strategy to visualize the distribution and identity of N-glycans in soybean root nodules at a cellular resolution. We additionally performed proteomics analysis to probe the potential correlation to proteome changes during symbiotic rhizobia-legume interactions. Our ion images reveal that intense N-glycosylation occurs in the sclerenchyma layer, and inside the infected cells within the infection zone, while morphological structures such as the cortex, uninfected cells, and cells that form the attachment with the root are less N-glycosylated. Notably, we observed different N-glycan profiles between soybean root nodules infected with wild type rhizobia and those infected with mutant rhizobia incapable of efficiently fixing atmospheric nitrogen. The majority of complex N-glycan structures, particularly those with characteristic Lewis-a epitopes, are overexpressed in the mutant nodules. Our proteomic results revealed that these glycans likely originated from proteins that maintain the redox balance crucial for proper nitrogen fixation, but also from enzymes involved in N-glycan and phenylpropanoid biosynthesis. These findings indicate possible involvement of Lewis-a glycans in these critical pathways during legume-rhizobia symbiosis.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Microbial growth under drought is confined to distinct taxa and modified by potential future climate conditions

Climate change increases the frequency and intensity of drought events, affecting soil functions including carbon sequestration and nutrient cycling, which are driven by growing microorganisms. Yet we know little about microbial responses to drought due to methodological limitations. Here, we estimate microbial growth rates in montane grassland soils exposed to ambient conditions, drought, and potential future climate conditions (i.e., soils exposed to 6 years of elevated temperatures and elevated CO 2 levels). For this purpose, we combined 18 O-water vapor equilibration with quantitative stable isotope probing (termed ‘vapor-qSIP’) to measure taxon-specific microbial growth in dry soils. In our experiments, drought caused >90% of bacterial and archaeal taxa to stop dividing and reduced the growth rates of persisting ones. Under drought, growing taxa accounted for only 4% of the total community as compared to 35% in the controls. Drought-tolerant communities were dominated by specialized members of the Actinobacteriota, particularly the genus Streptomyces. Six years of pre-exposure to future climate conditions (3 °C warming and + 300 ppm atmospheric CO 2 ) alleviated drought effects on microbial growth, through more drought-tolerant taxa across major phyla, accounting for 9% of the total community. Our results provide insights into the response of active microbes to drought today and in a future climate, and highlight the importance of studying drought in combination with future climate conditions to capture interactive effects and improve predictions of future soil-climate feedbacks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Catalysts by pyrolysis: Direct observation of chemical and morphological transformations leading to transition metal-nitrogen-carbon materials

Transition metal-nitrogen-carbon materials (M-N-C catalysts) are promising electrocatalysts in polymer electrolyte fuel cells (PEFCs) and electrolyzer applications. High temperature treatment in inert atmosphere (pyrolysis) is the essential, most common method for the synthesis of M-N-C catalysts and critical to achieve high electrocatalytic activity and electronic conductivity. To this day, despite many uses and successful implementations in materials manufacturing, pyrolysis has been an entirely empirical technology, with process control and optimization relying exclusively on “Edisonian” approach. The knowledge gap in the mechanism about how the precursor is being transformed into catalysts hinders further development of the M-N-C catalysts regardless of the precursor class and processing protocols. In this work, we probed the morphological evolution and chemical transformation of a nitrogen-containing charge transfer organic salt, mixed with transition metal (iron) salt and amorphous silica powder (precursor) during the pyrolysis process via a combination of in situ synchrotron and laboratory-based diagnostic techniques. The pyrolysis process is found to be divided into three stages. During a controlled temperature ramp, the selected organic N-C precursor (nicarbazin) began melting and decomposing just below 400 °C, forming a certain number of micrometer-scale pores and pathways. With increase in temperature from 400 °C to 900 °C, amorphous carbon domains started forming, and reduced (metallic) iron nanoclusters appeared, being dispersed uniformly throughout the carbonaceous matrix. When temperature advanced above 900 °C, graphitization of carbon commenced, associated with appearance and evolution of atomically dispersed metal-nitrogen moieties in the carbonaceous matrix. As the graphitization advanced further, a secondary process of agglomeration of metal nanoparticles occurred. Multi-analytical technique observations conducted here provide a base for rational design and optimization of M-N-C electrocatalysts via pyrolysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A laser powder bed fusion system for operando synchrotron x-ray imaging and correlative diagnostic experiments at the Stanford Synchrotron Radiation Lightsource

Laser powder bed fusion (LPBF) is a highly dynamic multi-physics process used for the additive manufacturing (AM) of metal components. Improving process understanding and validating predictive computational models require high-fidelity diagnostics capable of capturing data in challenging environments. Synchrotron x-ray techniques play a vital role in the validation process as they are the only in situ diagnostic capable of imaging sub-surface melt pool dynamics and microstructure evolution during LPBF-AM. In this article, a laboratory scale system designed to mimic LPBF process conditions while operating at a synchrotron facility is described. The system is implemented with process accurate atmospheric conditions, including an air knife for active vapor plume removal. Significantly, the chamber also incorporates a diagnostic sensor suite that monitors emitted optical, acoustic, and electronic signals during laser processing with coincident x-ray imaging. The addition of the sensor suite enables validation of these industrially compatible single point sensors by detecting pore formation and spatter events and directly correlating the events with changes in the detected signal. Experiments in the Ti–6Al–4V alloy performed at the Stanford Synchrotron Radiation Lightsource using the system are detailed with sufficient sampling rates to probe melt pool dynamics. X-ray imaging captures melt pool dynamics at frame rates of 20 kHz with a 2 µm pixel resolution, and the coincident diagnostic sensor data are recorded at 470 kHz. Furthermore, this work shows that the current system enables the in situ detection of defects during the LPBF process and permits direct correlation of diagnostic signatures at the exact time of defect formation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Effect of Anoxic Iron Corrosion on WIPP Brine Geochemistry FY23 Final Report (U)

A 280-day study was completed to evaluate the effect of zero-valent iron (Fe 0 ) on the Waste Isolation Pilot Plant (WIPP) brine geochemistry under anticipated reducing conditions. Hydrogen (H 2 ) gas is expected to be present in the repository after closure due to the anoxic corrosion of a vast quantity of iron contained in the waste forms disposed at WIPP; therefore, a background argon atmosphere containing H 2 was chosen for this study. WIPP groundwater brine pH and E h will impact the mobility and fate of plutonium within the repository. Modeling and laboratory results for Castile WIPP brine indicate that equilibrium fa values relative to the standard hydrogen electrode (SHE) are 40 mV more reducing (i.e., more negative) than those for Salado WIPP brine (-480 mV vs. -440 mV, respectively) because of the higher pH of the Castile brine (pH 9 .3 for Castile vs. pH 8.8 for Salado). The E h and pH data were corrected for the effects of high ionic strength. The experimental results for both brines are consistent with thermodynamic predictions using OLI Systems' Mixed Solvent Electrolyte chemical equilibrium model. The measured and corrected pH and E h data from this study are provided in Table ES-I and Table ES-2, respectively. The experimental study, with four test conditions in triplicate, was performed in a dual glovebox with a nominally 3 vol.% H 2 in argon atmosphere (target H 2 range: 3 ± I vol.%). Simulants containing MgO only ( experimental control) and MgO+Fe 0 (WIPP base case) were prepared for both the Salado and Castile brines. MgO was included in all simulants to account for the use of bulk magnesium oxide in the WIPP repository. Fe 0 was included in some simulants to incorporate the effects of the anoxic corrosion of iron and in-situ hydrogen generation in the study. The brine compositions were developed by Sandia National Laboratory (SNL; Xiong, 2008) and have been used in previous WIPP evaluations. The test method (agitation, etc.) is partially based on ASTM D3987-12. Twelve rounds of periodic measurements of pH and E h were performed over the course of the study. Chemical analysis results for liquids and solids (ICP-MS, ICP-ES, IC Anion, TIC, SEM-EDX) are consistent with the pH, E h , and thermodynamic modeling results. This study included the following conditions that deviate from anticipated post-closure conditions following brine intrusion, but were selected to facilitate bench-scale testing to validate modeling of pH and E h for the post-closure WIP P repository: an anoxic glove box atmosphere containing ≤ 4 vol. % H 2 vs. substantially higher H 2 gas concentrations assumed in the WIPP Performance Assessment (PA); a significantly higher liquid-to-solid test ratio compared to the much lower phase ratio anticipated in the WIP P repository; agitation of the simulant bottles to maximize mass transfer; and finally the use of Fe 0 reagents having a much greater surface area than expected in the WIP P repository. Non-representative conditions were chosen for various reasons such as: to provide bounding conservative results, to provide a margin of safety for testing, or to facilitate simulant sub-sampling and analysis. In a parallel effort, aqueous electrolyte thermodynamic models were developed for the synthetic Salado and Castile brines to inform the experimental design, facilitate laboratory data interpretation, and allow extension of evaluations beyond the parameters tested. Thermodynamic modeling simulations including the MgO and Fe 0 additives that are directly relevant to the experimental measurements (e.g., pH calibration curve, ORP corrections) are included in this report. The measured fa of the simulants was close to the OLI model predictions for both brines and was largely controlled by the background H 2 partial pressure in the vapor phase as well as H 2 generated in situ in the aqueous phase by the Fe 0 corrosion. The H 2 gas-phase concentration tested and thermodynamically evaluated was much lower than is assumed in the WIPP PA; however, H 2 (g) concentrations significantly below this level are still predicted to result in very reducing conditions. In conclusion: • The experimental results are consistent with thermodynamic model predictions for fa, pH, and the effects of high ionic strength. • Evidence to date suggests that the H2 concentration in the glovebox atmosphere ultimately determined the final E h values of the simulants and resulted in highly reducing conditions. As a result, little difference was observed between the control simulants containing only MgO and the WIPP base-case simulants that contained MgO and Fe 0 . • This test methodology is recommended for future studies evaluating WIPP repository conditions. The methodology includes: (1) background H 2 in argon with agitation ( or could alternatively include in-situ-generated H 2 in sealed bottles); (2) carefully measured and corrected ORP data ( with much effort focused on allowing the probes to fully stabilize); and (3) ionic-strength-corrected pH data. Other best practices, such as simulant sparging/handling, ORP probe replacement, etc., should also be considered. • The coupling of experimental studies and thermodynamic modeling is also highly recommended because these methods inform and direct one another leading to greater confidence in and understanding of the results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

BSM Studies Using Long-baseline Neutrino Experiment

The standard model of particle physics cannot account for the various physical phenomena present in nature. For instance, the visible matter constitutes only about 5$\%$ of the whole universe, and the remaining content is believed to be dark matter and dark energy. Unfortunately, the standard model does not provide us with a good candidate for dark matter. The leading dark matter candidate is weakly interacting massive particles (WIMPs) having a mass of less than 1 GeV. We will require a broad, fixed target neutrino experiment to probe the vast parameter space for the light-dark matter particle. NOvA is a high luminosity long-baseline fixed-target accelerator neutrino experiment at Fermilab. It can provide a potentially exciting probe in searching for signatures of DM scattering with electrons in its near detectors. We aim to search for the MeV-scale dark matter particles that might be generated within the NuMI beam and produce detectable electron scattering signals in the NOvA Near Detector. Not only in the dark matter sector, the standard model cannot explain the neutrino mass and mixings. The neutrino propagation in matter can be affected by non-standard interactions (NSI), which is beyond the standard model phenomena. The constraints coming from the NSI sectors can affect the standard oscillation parameters like atmospheric mixing angle $\theta_{23}$ and CP-phase $\delta_{CP}$.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

The vertical-velocity skewness in the atmospheric boundary layer without buoyancy and Coriolis effects

One of the main features of near-neutral atmospheric boundary layer (ABL) turbulence is the positive vertical velocity skewness $Sk_w$ above the roughness sublayer or the buffer region in smooth-walls. The $Sk_w$ variations are receiving renewed interest in many climate-related parameterizations of the ABL given their significance to cloud formation and to testing sub-grid schemes for Large Eddy Simulations (LES). The vertical variations of $Sk_w$ are explored here using wind tunnel and flume experiments collected above smooth, rough, and permeable-walls in the absence of buoyancy and Coriolis effects. These laboratory experiments form a necessary starting point to probe the canonical structure of $Sk_w$ as they deal with a key limiting case (i.e., near-neutral conditions). Diagnostic models based on cumulant expansions, realizability constraints, and constant mass flux approach routinely employed in the convective boundary layer as well as prognostic models based on third-order budgets are used to explain variations in $Sk_w$ for the idealized laboratory conditions. The failure of flux-gradient relations to model $Sk_w$ from the gradients of the vertical velocity variance σ$_w^2$ are explained and corrections based on models of energy transport offered. Novel links between the diagnostic and prognostic models are also featured, especially for the inertial term in the third-order budget of the vertical velocity fluctuation. The co-spectral properties of w′/σ w vs w′ 2 /σ$_w^2$ are also presented for the first time to assess the dominant scales governing $Sk_w$ in the inner and outer layers, where w′ is the fluctuating vertical velocity and σ w is the vertical velocity standard deviation.>

Boundary layer flow↗
DOE OSTI2025

Probing the elastic modulus and hardness of superionic boron cluster solid electrolytes

Polyhedral borane salts are highly tunable compounds with the potential to be used as solid electrolytes due to their high Li and Na superionic conductivity and relatively wide electrochemical stability window. In considering their application to all solid-state batteries, their mechanical properties play a critical role in their operation due to stresses the solid electrolyte is subjected to during battery operation. Density functional theory (DFT) calculations have provided an initial assessment of bulk and elastic moduli for some selected boron cluster solid electrolytes, but direct measurements are still scarce. Here, in this paper, we report the elastic moduli and hardnesses of LiCB 11 H 12 , LiCB 9 H 10 , NaCB 11 H 12 , and NaCB 9 H 10 for the first time using nanoindentation continuous stiffness method (CSM) measurements under inert atmosphere. Experimental modulus values ranging 8.8–12.3 GPa and hardness values ranging 0.15–0.38 GPa are lower than that of other inorganic solid-state electrolytes such as oxide- and sulfide-based solid electrolytes. DFT calculations on the expected moduli of these compounds are also presented and discussed. Analysis of the indentation plasticity index reveals that these compounds have higher plasticity index compared to other common oxide and sulfide solid electrolytes. According to the calculated Pugh's ratio, all compounds in this study except LiCB 11 H 12 are considered ductile.

25 ENERGY STORAGE↗
DOE OSTI2023

Throughfall-Reduction Drying Effects on Soil Respiration, Moisture, and Temperature in Four Distinct Lowland Panamanian Forests from 2015-2022

Objectives: Climatic drying is predicted for many tropical forests, yet effects on soil properties across moisture and soil gradients within tropical forests remain poorly characterized, hampering predictions of forest-climate feedbacks. We hypothesized that throughfall reduction (i.e. chronic drying) would suppress soil CO2 fluxes (i.e., respiration) in already-drier tropical forests by further reductions in soil moisture, but increases CO2 fluxes in wetter tropical forests by alleviating anaerobiosis and soil saturation. We conducted a field study in four distinct lowland Panamanian forests that vary in background rainfall and soil fertility. In each forest we constructed throughfall reduction structures that reduce moisture inputs to plots by ~50% (see methods). In drying and paired control plots we measured soil CO2 fluxes, soil moisture (volume/volume), soil temperature (°C), air temperature (°C), and forest floor biomass during wet-dry cycles (2015 – 2022). We also collected litterfall biomass and surveyed all tree species for diameter at breast height (dbh), and identified tree species in 2018 and 2019.Results:We found that soil moisture peaked in the wet season and declined in the dry season. Measured soil CO2 fluxes declined in the dry season and peaked in the early wet season ahead of peak soil moisture, resulting in a lower soil moisture optimum for respiration than previously modeled. Chronic throughfall exclusion also suppressed soil moisture across the four forests, and also initially suppressed soil CO2 fluxes across forests. There was sustained suppression of soil CO2 fluxes after four years in the wettest forest only (-28 ± 4% during the dry season), but elevated soil CO2 fluxes in a fertile forest after four years (+75 ± 28% during the late wet season). The unexpected negative drying effect in the wettest, most infertile forest could have resulted from reduced vertical flushing of nutrients into soils, as the drying effect increased with time. Including hydro-nutrient interactions in ecosystem models could improve predictions of tropical forest-climate feedbacks. Datasets included: Datasets included here include .csv and .xls files for soil respiration (carbon dioxide flux) collected using the LiCor (see methods), air temperature °C , soil moisture (vl/vl), and soil temperature °C. Soil moisture and soil temperature were collected at 0-10cm depths using hand-held probes (see methods). Data are on ~3 week timescales from 2015-2022 with some gaps. There is also a .kml file that includes coordinates for all 32 plots included in the study of four forests (n = 4 throughfall reduction and n = 4 control plots per site). No special software is needed to open these files.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Calorimetric Detection of Dark Matter

Dark matter direct detection experiments are designed to look for the scattering of dark matter particles that are assumed to move with virial velocities $\sim 10^{-3}$. At these velocities, the energy deposition in the detector is large enough to cause ionization/scintillation, forming the primary class of signatures looked for in such experiments. These experiments are blind to a large class of dark matter models where the dark matter has relatively large scattering cross-sections with the standard model, resulting in the dark matter undergoing multiple scattering with the atmosphere and the rock overburden, and thus slowing down considerably before arriving at underground detectors. We propose to search for these kinds of dark matter by looking for the anomalous heating of a well shielded and sensitive calorimeter. In this detector concept, the dark matter is thermalized with the rock overburden but is able to pierce through the thermal shields of the detector causing anomalous heating. Using the technologies under development for EDELWEISS and SuperCDMS, we estimate the sensitivity of such a calorimetric detector. In addition to models with large dark matter - standard model interactions, these detectors also have the ability to probe dark photon dark matter.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Layers Can Be Deceiving: A Hopping Model for Small Molecule Diffusion in TATB Crystal

Sorption of small molecule gases in materials can play a significant role in their long‐term stability and compatibility within multi‐material assemblies. While many material properties of the insensitive high explosive TATB (1,3,5‐triamino‐2,4,6‐trinitrobenzene) are well understood, very little is known regarding its permeability to gases. TATB crystal exhibits a graphitic‐like layered packing structure that evokes a mental schema in which the layers form nanoscopic channels, but it is unclear whether this structure promotes gas transport. Here, we use molecular dynamics (MD) simulations to predict transport of small molecules through TATB single crystal. An approach to fit classical force fields is developed to model TATB interactions with H 2 O, He, Ne, and Ar, which is then combined with steered MD to probe gas transport along selected directions in the crystal. We find that small molecule transport occurs via a hopping mechanism that exhibits distinct jumps between interstitial sites and is substantially faster normal to the layers as compared to through them. This result stems from the finding that intralayer junctions between adjacent TATB molecules are the most stable interstitial sites and that energetic barriers are lower for hopping between adjacent layers. An empirical model for diffusion rate based on the MD data shows that the rate decays exponentially with increasing molecular radius and is negligibly small for all molecules larger than He, including common atmospheric gases. These findings have implications for the interpretation of experiments that measure surface area, material response to extreme conditions, and are expected to help constrain models for material aging.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Characterization of high-frequency waves in the Martian magnetosphere

Context.Various high-frequency waves in the vicinity of upper-hybrid and Langmuir frequencies are commonly observed in different space plasma environments. Such waves and fluctuations have been reported in the magnetosphere of the Earth, a planet with an intrinsic strong magnetic field. Mars has no intrinsic magnetic field and, instead, it possesses a weak induced magnetosphere, which is highly dynamic due to direct exposure to the solar wind. In the present paper, we investigate the presence of high-frequency plasma waves in the Martian plasma environment by making use of the high-resolution electric field data from the Mars Atmosphere and Volatile Evolution missioN (MAVEN) spacecraft. Aims.This study aims to provide conclusive observational evidence of the occurrence of high-frequency plasma waves around the electron plasma frequency in the Martian magnetosphere. We observe two distinct wave modes with frequency below and above the electron plasma frequency. The characteristics of these high-frequency waves are quantified and presented here. We discuss the generation of possible wave modes by taking into account the ambient plasma parameters in the region of observation. Methods.We have made use of the medium frequency (100 Hz–32 kHz) burst mode-calibrated electric field data from the Langmuir Probe and Waves instrument on board NASA’s MAVEN mission. Due to the weak magnetic field strength, the electron gyro-frequency is much lower than the electron plasma frequency, which implies that the upper-hybrid and Langmuir waves have comparable frequencies. A total of 19 wave events with wave activities around electron plasma frequency were identified by examining high-resolution spectrograms of the electric field. Results.These waves were observed around 5 LT when MAVEN crossed the magnetopause boundary and entered the magnetosheath region. These waves are either a broadband- or narrowband-type with distinguishable features in the frequency domain. The narrowband-type waves have spectral peak above the electron plasma frequency. However, in the case of broadband-type waves, the spectral peak always occurred below the electron plasma frequency. The broadband waves consistently show a periodic modulation of 8–14 ms. Conclusions.The high-frequency narrowband-type waves observed above the electron plasma frequency are believed to be associated with upper-hybrid or Langmuir waves. However, the physical mechanism responsible for the generation of broadband-type waves and the associated 8–14 ms modulation remain unexplained and further investigation is required.

Astronomy & Astrophysics↗
DOE OSTI2021

Straight lightning as a signature of macroscopic dark matter

Macroscopic dark matter (macros) is a broad class of alternative candidates to particle dark matter. These candidates would transfer energy to matter primarily through elastic scattering. A sufficiently large macro passing through the atmosphere would produce a straight channel of ionized plasma. If the cross-section of the macro is σx ≳ 6 × 10 –9 cm 2 , then under atmospheric conditions conducive to lightning (eg. a thunderstorm) the plasma channel would be sufficient to seed a lightning strike with a single leader. This is entirely unlike ordinary bolt lightning in which a long sequence of hundreds or thousands of few-meter-long leaders are strung together. This macro-induced lightning would be extremely straight, and thus highly distinctive. Neither wind shear nor magnetohydrodynamic instabilities would markedly spoil its straightness. The only photographically documented case of a straight lightning bolt is probably not straight enough to have been macro-induced. We estimate the region of macro parameter space that could be probed by a search for straight lightning from the number of thunderstorms happening on Earth at any time. In conclusion, we also estimate the parameter space that can be probed by carefully monitoring Jupiter, e.g. using the Hubble Space Telescope.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

A two-fluid solar-wind model with intermittent Alfvénic turbulence

In one of the leading theories for the origin of the solar wind, photospheric motions launch Alfvén waves (AWs) that propagate along open magnetic-field lines through the solar atmosphere and into the solar wind. The radial variation in the Alfvén speed causes some of the AWs to reflect, and counter-propagating AWs subsequently interact to produce Alfveńic turbulence, in which AW energy cascades from long wavelengths to short wavelengths and dissipates, heating the plasma. In this paper we develop a one-dimensional two-fluid solar-wind model that includes Alfvénic turbulence, proton temperature anisotropy and a novel method for apportioning the turbulent heating rate between parallel proton heating, perpendicular proton heating and electron heating. We employ a turbulence model that accounts for recent observations from NASA’s Parker Solar Probe, which find that AW fluctuations in the near-Sun solar wind are intermittent and less anisotropic than in previous models of anisotropic magnetohydrodynamic turbulence. Our solar-wind model reproduces a wide range of remote observations of the corona and in-situ measurements of the solar wind, and our turbulent heating model consists of analytic equations that could be usefully incorporated into other solar-wind models and numerical models of more distant astrophysical plasmas.

astrophysical plasmas↗
DOE OSTI2020

Spatial defects nanoengineering for bipolar conductivity in MoS 2

Understanding the atomistic origin of defects in two-dimensional transition metal dichalcogenides, their impact on the electronic properties, and how to control them is critical for future electronics and optoelectronics. Here, we demonstrate the integration of thermochemical scanning probe lithography (tc-SPL) with a flow-through reactive gas cell to achieve nanoscale control of defects in monolayer MoS 2 . The tc-SPL produced defects can present either p- or n-type doping on demand, depending on the used gasses, allowing the realization of field effect transistors, and p-n junctions with precise sub-μm spatial control, and a rectification ratio of over 10 4 . Doping and defects formation are elucidated by means of X-Ray photoelectron spectroscopy, scanning transmission electron microscopy, and density functional theory. We find that p-type doping in HCl/H 2 O atmosphere is related to the rearrangement of sulfur atoms, and the formation of protruding covalent S-S bonds on the surface. Alternatively, local heating MoS 2 in N 2 produces n-character.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Autonomous Infrared and Small (Wide) Angle X-Ray Scattering (IR-S(W)AXS) Capability

Thin water films are 2-D, nanoconfined layers that form on solid surfaces exposed to humid atmospheres—environments ubiquitous across catalysis, corrosion science, soil science, and subsurface geochemistry. At relative humidity (RH) values below saturation, these films are Å–nm thick and exhibit properties that differ sharply from bulk water, including disrupted H-bonding and impeded mass transport. Owing to their high surface-to-volume ratio, dissolution of the solid can rapidly drive strong supersaturation with respect to secondary phases. Reactivity in thin water films is highly sensitive to film thickness, and critically, thickness evolves during reaction because the hygroscopicity of the interfacial system changes as ions accumulate or diminish in the film and as reaction products transform. To accurately probe and control these dynamics, a capability is needed that can measure and automatically maintain a constant water-film thickness while simultaneously monitoring solid dissolution, nucleation, and growth. This project developed an autonomous Infrared/Small Angle X-ray Scattering-Wide Angle X-ray Scattering (IR/(W)SAXS) for investigating reactivity in thin water films on solid surfaces exposed to humidified gases. The capability consists of an IR spectrometer, a (W)SAXS instrument, and a mass flow controller system for generating variably humidified gas flows to a custom reaction cell. Progress on each of the major components of the capability are detailed below.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

How a Formate Dehydrogenase Responds to Oxygen: Unexpected O 2 Insensitivity of an Enzyme Harboring Tungstopterin, Selenocysteine, and [4Fe–4S] Clusters

The reversible two-electron interconversion of formate and CO 2 is catalyzed by both nonmetallo- and metallo-formate dehydrogenases (FDHs). The latter group comprises molybdenum- or tungsten-containing enzymes with the metal coordinated by two equivalents of a pyranopterin cofactor, a cysteinyl or selenocysteinyl (Sec) ligand supplied by the polypeptide, and a catalytically essential terminal sulfido ligand. In addition, these biocatalysts incorporate one or more [4Fe–4S] clusters for facilitating long-distance electron transfer. However, an interesting dichotomy arises when attempting to understand how the metallo-FDHs react with O 2 . Whereas existing scholarship portrays these enzymes as being unable to perform in air due to extreme O 2 lability of their metal centers, studies dating as far back as the 1930s emphasize that some of these systems exhibit formate oxidase (FOX) activity, coupling formate oxidation to O 2 reduction. Therefore, to reconcile these conflicting views, we explored context-dependent functional linkages between metallo-FDHs and their cognate electron acceptors within the same organism vis-à-vis catalysis under atmospheric O 2 . Here, we report the discovery and characterization of an O 2 -insensitive FDH2 from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH) that ligates tungsten, Sec, and four [4Fe–4S] clusters. By advancing a robust expression platform for its recombinant production, we eliminate both the requirement of nitrate or azide during purification and reductive activation with thiols and/or formate prior to catalysis. Because the distinctive spectral signatures of formate-reduced DvH-FDH2 remain invariant under anaerobic and aerobic conditions, we benchmarked the enzyme activity in air, identifying CO 2 as the catalytic product. Full reaction progress curve analysis discloses a high catalytic efficiency when probed with a high-potential artificial electron acceptor. Furthermore, we show that DvH-FDH2 enables near-stoichiometric hydrogen peroxide production without superoxide release to achieve O 2 insensitivity. Notably, simultaneous electron transfer to cytochrome c and O 2 reveals that metal-based electron bifurcation is operational in this system. Taken together, our work proves the co-occurrence of redox bifurcated FDH and FOX activities within a metalloenzyme scaffold. These findings set the stage for uncovering previously unknown O 2 -insensitive flavin-based electron bifurcation mechanisms, as well as for developing authentic formate/air biofuel cells, engineering O 2 -stable FDHs and biohybrid metallocatalysts, and discerning formate bioenergetics of gut microbiota.

13C NMR↗
DOE OSTI2023

Probing the Behavior of Composition‐Tunable Ultrathin PtNi Nanowires for CO Oxidation and Small‐Molecule Electrocatalytic Reactions

We have successfully synthesized ultrathin nanowires of pure Pt, Pt 99 Ni 1 , Pt 9 Ni 1 , and Pt 7 Ni 3 using a modified room-temperature soft-template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt 7 Ni 3 samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm 2 respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre-reduction treatment; however, after annealing in H 2 , we detected significantly improved CO 2 formation for both Pt 9 Ni 1 and Pt 7 Ni 3 motifs. These observations highlight the importance of pre-treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x-ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt-rich shell coupled with a Ni-rich core. Here, we also observed that the degree of alloying within the nanowires increased after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.

36 MATERIALS SCIENCE↗