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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The charge reduction rate for multiply charged polymer ions via ion–ion recombination at atmospheric pressure

The charge reduction of multiply charged macromolecular ions via recombination with small ions in the gas phase is commonly employed to modulate the charge on macromolecules prior to mass spectrometric and mobility analyses. We employ a recently developed continuum-Molecular Dynamics (MD) calculation approach to determine the recombination rate coefficient of multiply charged (1 to 7 excess positive charged) polyethylene glycol ions (mass of 4600 Da) with smaller singly charged anions, modeled as NO 2 – ions. The continuum-MD approach accounts explicitly for the influence of the background gas on the recombination process, accounts explicitly for ion translational, vibrational, and rotational motion, and enables recombination rate coefficient calculation in nitrogen near atmospheric pressure, wherein neither low pressure nor high pressure recombination theories are strictly applicable. Continuum-MD simulations yield recombination rate coefficients near 3.9 × 10 –14 m 3 s –1 for singly charged ions, increasing to 3.0 × 10 –11 m 3 s –1 for the +7 ion. Pre-existing collision rate coefficient expressions for rigid ions are found to be within a factor of 2–5 of calculations for all charge states, but their use requires knowledge of an appropriate collision distance, which is not well-defined for flexible polymer ions. Continuum-MD-inferred rate coefficients are incorporated into a model of charge reduction, and the charge state distribution versus anion concentration determined with it is compared to charge reduction measurements made via atmospheric pressure differential mobility analysis. Furthermore, good agreement is observed between simulations and experiments; although results are extremely sensitive to the recombination rate coefficients, experimental results are bound by models utilizing rates within a factor of 2 (0.5–2.0×) of the continuum-MD rates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

The Role of Interfaces and Charge for Chemical Reactivity in Microdroplets

A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here, in this work, we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.

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

Near L-edge Single and Multiple Photoionization of Doubly Charged Iron Ions

Using the photon-ion merged-beams technique at a synchrotron light source, we have measured relative cross sections for single and up to five-fold photoionization of Fe 2+ ions in the energy range of 690-920 eV. This range contains thresholds and resonances associated with ionization and excitation of 2p and 2s electrons. Calculations were performed to simulate the total absorption spectra. The theoretical results show very good agreement with the experimental data, if overall energy shifts of up to 2.5 eV are applied to the calculated resonance positions and assumptions are made about the initial experimental population of the various levels of the Fe 2+ ([Ar]3d 6 ) ground configuration. Furthermore, we performed extensive calculations of the Auger cascades that result when an electron is removed from the 2p subshell of Fe 2+ . These computations lead to a better agreement with the measured product-charge-state distributions as compared to earlier work. We conclude that the L-shell absorption features of low-charged iron ions are useful for identifying gas-phase iron in the interstellar medium and for discriminating against the various forms of condensed-phase iron bound to composite interstellar dust grains.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Pulsed laser synthesis of mesoporous metal chalcogenide thin films

Mesoporous films of the metal chalcogenide B-FeSe were grown on MgO substrates by KrF pulsed laser deposition (PLD) in an argon background. At 100 mTorr, gated intensified charge-coupled device imaging and ion probe measurements showed that the plasma plume responsible for crystal growth initially comprised three components, with distinct expansion velocities. Plume interactions with the substrate heater and ablation target gave rise to complex dynamics, including collisions between the charged leading edge—rebounding between the substrate and the target—and slower-moving species in the plume interior. Film growth was dominated by species with kinetic energies ≤0.5 eV/atom. X-ray reflectivity revealed that films grown in this environment—with a substrate temperature of 350 ° C, a laser fluence of 1.0 J cm −2 , and a 7.5 mm 2 spot area—formed a porous framework with 15% porosity. Atomic force microscopy showed surface features that suggest pore sizes below 100 nm. X-ray diffraction indicated that the porous films were epitaxial with respect to the substrate and likely grew by oriented-attachment of gas-phase molecular clusters or very small nanoparticles, in contrast to the conventional epitaxy of vacuum films from atomic constituents. The in-plane orientation of the mesoporous films was B-FeSe [100]||[110] MgO, attributed to the soft landing of pre-formed crystallites on the MgO substrates, where protruding Se rows of B-FeSe aligned with corrugations of the MgO surface. In conclusion, this work implies that growth of candidate electrocatalyst materials by PLD in inert gas background may allow mesoporous frameworks with a single crystallographic orientation that expose specific crystal facets for electrochemical reactions and active site engineering.

cluster epitaxy↗
DOE OSTI2025

Real-Time Detection of Hydrogen and Ammonia Isotopologues for Impurity Removal and Recovery of Tritium

To accommodate gas measurements for impurity removal and recovery of tritium, a silver-coated optical or waveguide is employed for collecting Raman scattered signals to determine relative hydrogen and ammonia isotopologue populations in real time. The data and results presented here demonstrate an analytical methodology for the analysis of four ammonia and three hydrogen isotopologues in a hydrogen–deuterium exchange reaction by gas phase Raman spectroscopy. Standard chemometric modeling techniques effectively unravel the signatures of the isotopologues involved observed here; however, a sophisticated quantum chemical approach supports the spectral assignments. An interpretation of the data presented here can emphasize the practicality and reliability of the gaseous monitoring system in complex chemical environments for the hydrogen fuel economy as well as the more distant energy source from a facility that handles tritium. There are still considerable concerns about the measurement of tritium in isotope separation and radiological impurities from gas processing. A common impurity in gas processing is ammonia, which can form readily in the presence of nitrogen and tritium. Substituted ammonia (NQ 3 ), where Q = H, D, or T, is traditionally removed through getters or diffusers along with other non-hydrogen contaminants. A preferable analytical approach is noninvasive and can be deployed for real-time process evaluation in radiological environments.

Ammonia↗
DOE OSTI2024

New Instrument for Time-Resolved OH and HO 2 Quantification in High-Pressure Laboratory Kinetics Studies

Here, we have constructed a new time-resolved high-pressure fluorescence assay by gas expansion (HP-FAGE) apparatus, optimized for the detection of OH and HO 2 radicals in complex gas-phase reactions. The new instrument fills a gap in the existing experimental toolkit for chemical kinetics by enabling the quantification of two key reactive species with microsecond time resolution from high-pressure sources, which was previously not attainable. The HP-FAGE is interfaced with a flow reactor, designed for pressures up to 100 bar and temperatures up to 1000 K, in which reactions are initiated by laser photolysis of radical precursors at repetition rates of 1–10 Hz. The HP-FAGE samples gas out of the reactor into a miniature FAGE chamber, where OH is detected by resonant laser-induced fluorescence using a time-delayed probe laser pulse. HO 2 is converted to OH via reaction with NO and then detected by OH fluorescence. The novel FAGE design places the probe region very close to the gas expansion, minimizing the transport time of sampled molecules and resulting in time resolution better than 20 μs for both OH and HO 2 . We calibrate the sensitivity of HP-FAGE, validate its performance with measurements of well-known reaction kinetics (OH + CH 4 , OH + OH, OH + HO 2 , and HO 2 + HO 2 ), and discuss prospects for its future use.

calibration↗
DOE OSTI2020

Effect of hydride vapor phase epitaxy growth conditions on the degree of atomic ordering in GaInP

We report a systematic study of CuPt-type ordering in hydride vapor phase epitaxy (HVPE)-grown Ga 0.5 In 0.5 P. Selected-area electron diffraction reveals ordering in samples grown on (001) GaAs substrates offcut toward (1$\overline{1}$1)B. The ordering is single-variant, occurring only on (1$\overline{1}$1)B planes and not on ($\overline{1}$11)B. Quantitative analysis of the order parameter by high-resolution x-ray diffraction (HRXRD) indicates that ordering increases with deposition temperature in samples grown at 600–700 °C with a constant gas-phase V/III ratio ~3. Ordering increases with V/III ratio in the range of 1.3–6.7 at a constant deposition temperature of 650°C. Photoluminescence measurements correlate the order parameter with Ga0.5In0.5P bandgap contraction, though the contraction is larger than expected based on the magnitude of order parameters measured by HRXRD. A possible reason for this discrepancy is that the photoluminescence emission occurs in the lower bandgap ordered domains, which are small and evenly dispersed throughout the material. We also show that the degree of ordering decreases with growth rate, disappearing at ~60 µm/h. The HVPE-grown material exhibits a generally weaker ordering than organometallic vapor phase epitaxy (OMVPE)-grown material, likely due to the moderate V/III ratios employed, in contrast to the V/III ratios in the 100s typical of OMVPE. However, the tendency for ordering to increase with V/III ratio suggests that the same dimer-induced stress mechanism used to explain the occurrence of ordering in OMVPE-grown material also applies to HVPE. The tendencies for ordering to increase with deposition temperature and decrease with growth rate show that kinetics limit the degree of ordering, also in agreement with OMVPE trends.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane

Boron–containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. Here, we combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface–mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure–dependent relative formation of the main product propylene and by–product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium–based catalysts.

03 NATURAL GAS↗
DOE OSTI2026

Beyond Mass and Multiscale Environments: What Shapes Low Surface Brightness Galaxies? Evidence from MaNGA

The origin of low surface brightness (LSB) galaxies remains a key open question in galaxy formation, reflecting the balance between internal mechanisms and environmental influence. Using MaNGA integral-field spectroscopy, we investigate whether LSB and high surface brightness (HSB) galaxies of comparable stellar mass (9 < logM * < 10) occupy distinct environments or differ primarily through internal evolution. Our late-type sample comprises 113 central and 29 satellite LSB galaxies, and 374 central and 142 satellite HSB galaxies. We characterize environments on scales from ∼100 kpc to 10 Mpc, analyzing radial profiles of stellar mass surface density (Σ * ), star formation activity, and gas-phase metallicity. Central LSB and HSB galaxies inhabit similarly low-density large-scale (>200 kpc) environments, but LSB galaxies are more isolated on small scales (∼100 kpc). Even after matching in stellar mass and environment, LSB galaxies show systematically lower Σ * , Σ SFR , and metallicities, often hosting diffuse, weakly star-forming bulges embedded in extended disks. These results indicate that LSB structure and star formation are not primarily governed by a large-scale environment or halo mass. While secondary halo properties such as spin, concentration, or gas accretion history are often invoked, their environmental dependence appears weak. Instead, LSB–HSB differences for centrals likely reflect divergent assembly or interaction histories and internal processes—such as angular momentum-driven disk evolution or inefficient gas conversion—largely decoupled from a large-scale environment. Nonetheless, the environment still influences the observed star formation and chemical differences between central and satellite LSB galaxies.

Shen, Mengting [Xiamen University (China); SDSS Co↗
DOE OSTI2022

A Multiwavelength View of IC 860: What Is in Action inside Quenching Galaxies

We present a multiwavelength study of IC 860, a nearby post-starburst galaxy at the early stage of transitioning from blue and star forming to red and quiescent. Optical images reveal a galaxy-wide, dusty outflow originating from a compact core. We find evidence for a multiphase outflow in the molecular and neutral gas phase from the CO position–velocity diagram and NaD absorption features. We constrain the neutral mass outflow rate to be ~0.5 M ⊙ yr -1 , and the total hydrogen mass outflow rate to be ~12 M ⊙ yr -1 . Neither outflow component seems able to escape the galaxy. We also find evidence for a recent merger in the optical images, CO spatial distribution, and kinematics, and evidence for a buried active galactic nucleus in the optical emission line ratios, mid-IR properties, and radio spectral shape. The depletion time of the molecular gas reservoir under the current star formation rate is ~7 Gyr, indicating that the galaxy could stay at the intermediate stage between the blue and red sequence for a long time. Thus the timescales for a significant decline in star formation rate (quenching) and gas depletion are not necessarily the same. Our analysis supports the quenching picture where outflows help suppress star formation by disturbing rather than expelling the gas and shed light on possible ongoing activities in similar quenching galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Pore connectivity influences mass transport in natural rocks: Pore structure, gas diffusion and batch sorption studies

For this work, six rocks (one granodiorite, one limestone, two chalks, one mudstone, and one dolostone) with different extents of heterogeneity at six different particle sizes (from 75 to 8000 μm) were studied to describe the effects of pore connectivity on mass transport. The methods applied were (i) porosity measurement of granular rocks, (ii) analyses of gas-phase diffusive transport in a bed of packed particles, along with a solid quartz method at these six particle sizes being developed to identify the contribution of intraparticle diffusion, and (iii) batch sorption tests of multiple ions (anions and cations) with subsequent analyses of inductively coupled plasma-mass spectrometry. Granular porosity measurement results reveal that with decreasing particle sizes, the effective porosities for the “heterogenous” group of rocks (Grimsel granodiorite and Edwards limestone) increase, whereas the porosities of another “homogeneous” group (two Israel chalk samples, Japan mudstone, and Wyoming dolostone) remain constant. Gas diffusion results show that the intraparticle gas diffusion coefficient among these two sample groups, varying in the magnitude of 10 -8 to 10 -6 m 2 /s, are not directly correlated to the porosity differences. Moreover, the batch sorption work displays a different affinity of rocks for various tracers. For Grimsel granodiorite, Japan mudstone, and Wyoming dolostone, the adsorption capacity of Sm 3+ and Eu 3+ increases as the particle size decreases. In general, this integrated research of grain size distribution, granular rock porosity, intraparticle diffusivity, and ionic sorption capacity gives insights into the pore connectivity effect on both physical and chemical transport behaviors for different lithologies and/or different particle sizes.

58 GEOSCIENCES↗
DOE OSTI2022

Particle trapping, size-filtering, and focusing in the nonthermal plasma synthesis of sub-10 nanometer particles

Low-pressure nonthermal flowing plasmas are widely used for the gas-phase synthesis of nanoparticles and quantum dots of materials that are difficult or impractical to synthesize using other techniques. To date, the impact of temporary electrostatic particle trapping in these plasmas has not been recognized, a process that may be leveraged to control particle properties. Furthermore, we present experimental and computational evidence that, during their growth in the plasma, sub-10 nm silicon particles become temporarily confined in an electrostatic trap in radio-frequency excited plasmas until they grow to a size at which the increasing drag force imparted by the flowing gas entrains the particles, carrying them out of the trap. We demonstrate that this trapping enables the size filtering of the synthesized particles, leading to highly monodisperse particle sizes, as well as the electrostatic focusing of the particles onto the reactor centerline. Understanding of the mechanisms and utilization of such particle trapping will enable the design of plasma processes with improved size control and the ability to grow heterostructured nanoparticles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Continuous caustic aqueous phase electrochemical reforming (CAPER) of ethanol for producing compressed hydrogen

Caustic Aqueous Phase Electrochemical Reforming (CAPER) of ethanol produces pure compressed H 2 at lower voltages, temperatures, and energy requirements than conventional electrolysis, while capturing carbonaceous products. The CAPER flow reactor consists of stainless steel endplates, stainless steel current collectors, and a Teflon flow field. The electrodes are prepared using commercial palladium nanoparticles on carbon support for the anode and platinum nanoparticles on carbon support for the cathode. The catalyst metal loading was 1 mgcm –2 on a 10cm 2 carbon cloth for both electrodes. Our CAPER reactor produces pure H 2 at 80bar and 80°C applying voltages at ≤0.5V. The only gas-phase product detected was H 2 and any carbonaceous products were contained in the liquid phase. The H 2 was produced with 97±4% faradaic efficiency. Further, operating at smaller electrode separation distances (4mm) and 80°C increased the current density. The highest lower heating value efficiency achieved was 28% at a flow rate of 0.05mLmin –1 and an applied voltage of 0.5V. The compressed H 2 was produced at ≤20 kWh kg –1 , which is much lower than electrolysis systems that require upwards of 50 kWh kg –1 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Faradaic efficiency in protonic-ceramic electrolysis cells

Abstract Proton-conducting ceramics (e.g. doped barium zirconates or cerates) are typically mixed ionic-electronic conductors (MIECs). The electronic conduction, typically in the form of positively charged small polarons or electron holes, leads to ‘electronic leakage.’ In an ideal steam-electrolysis cell, one gas-phase H 2 molecule is produced from every two electrons delivered from an external power source. In other words, such ideal behavior achieves 100% faradaic efficiency. However, the electronic flux associated with MIEC membranes contributes to reduced faradaic efficiency. The present paper develops a model that predicts the behavior of faradaic efficiency as a function of electrolysis-cell operating conditions. Although the model framework is more general, the paper focuses on the behavior of a cell based upon a BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3 − δ (BCZYYb) membrane. The study predicts the effects of operating conditions, including temperature, pressure, and gas compositions.

Zhu, Huayang↗
DOE OSTI2024

EWTN: Quantifying Mass Transport to Enable Water Electrolyzer Architectures with Low Flow-Rate Sensitivity

To develop cost-effective and high-performing polymer electrolyte water electrolyzers (PEWEs) for gigawatt-scale applications, researchers have focused on reducing precious metal catalyst loadings and optimizing porous transport layers. However, the performance of PEWEs is also affected by system architecture. Mass transport losses are dependent on localized architecture and material interactions. In-situ measurements, such as current density distribution maps have demonstrated advantages in understanding the intricate characteristics and influence of two-phase flow within PEWEs. This study proposes the parameter of effective water transport number (EWTN) as a quantitative tool to investigate such current density distribution (CDD) measurements for PEWEs. Results show that higher flow-rates have EWTN values of 0.95 and above, indicating no mass transport limitations; while lower flow-rates with large gradients CDD have EWTN values between 0.6-0.8, indicating mass transport limited conditions. The new analysis also identified a correlation between mass transport losses due to bubble accumulation, membrane hydration, and ohmic overpotentials. To address these limitations, an unitized pin-type LGDL/flow-field design was developed, which effectively prevents local gas phase accumulation, resulting in improved mass transport characteristics. The results of this work show reduced flow-rate sensitivity with the pin-type architecture and ∼13% increased performance at 0.24 ml / min / cm 2 .

Electrochemistry↗
DOE OSTI2021

Computational Fermi Level Engineering and Doping-Type Conversion of Mg:Ga 2 O 3 via Three-Step Synthesis Process

Gallium oxide (Ga 2 O 3 ) is being actively explored for electronics that can operate at high power, temperature, and frequency as well as for deep-ultraviolet optoelectronics and other applications due to its ultra-wide bandgap (UWBG) and low projected fabrication cost of large-size and high-quality crystals. Efficient n-type doping of monoclinic beta-phase of Ga 2 O 3 has been achieved, but p-type doping faces fundamental obstacles due to compensation, deep acceptor levels, and the polaron transport mechanism of free holes. However, aside from the challenges of achieving p-type conductivity, plenty of opportunity exists to engineer the position of the Fermi level for improved design of Ga 2 O 3 -based devices. We use first-principles defect theory and defect equilibrium calculations to simulate a three-step growth-annealing-quench synthesis protocol for hydrogen-assisted Mg doping in ß-Ga 2 O 3 . The simulations take into account the gas phase equilibrium between H 2 , O 2 , and H 2 O, which determines the H chemical potential. We predict Ga 2 O 3 doping-type conversion to a net p-type regime after growth under reducing conditions in the presence of H2 followed by O-rich annealing, which is a similar process to Mg acceptor activation by H removal in GaN. For equilibrium annealing with re-equilibration of compensating O vacancies, there is an optimal temperature that maximizes the Ga 2 O 3 net acceptor density for a given Mg doping level; the acceptor density is further increased in the non-equilibrium annealing scenario without re-equilibration. After quenching to operating temperature, the Ga 2 O 3 Fermi level drops below mid-gap down to about 1.5 eV above the valence band maximum, creating a significant number of uncompensated neutral Mg Ga 0 acceptors. The resulting free hole concentration in Ga 2 O 3 is very low even at elevated operating temperature (~10 8 cm -3 at 400°C) due to the deep energy level of these Mg acceptors, and hole conductivity is further impeded by the polaron hopping mechanism. However, the Fermi-level reduction and suppression of free electron density in this doping-type converted (NA>ND) Ga 2 O 3 material are important for improved designs of Ga 2 O 3 electronic devices. These results illustrate the power of computational predictions not only for new materials but also for their synthesis science.

36 MATERIALS SCIENCE↗