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At least 343 records · Page 19

All sources NASA NTRS DOE OSTI

DOE OSTI2021

Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Abstract Metal carbonyl clusters (MCC's) are atomically defined nanomaterials which can be characterized using the precise tools of molecular (electro)chemistry. HER mechanisms involve two proton transfer (PT) steps in the catalytic cycle. For HER catalyzed by [Co 11 C 2 (CO) 23 ] 3− ( 1 3− ), cyclic voltammetry measurements were used to determine the rate for PT1 as k PT1 =3×10 8 M −1 s −1 , whereas the rate for PT2 is k PT2 =3.7×10 3 M −1 s −1 . The fast, diffusion‐limited rate for PT1 is consistent with a previous report describing [Co 13 C 2 (CO) 24 ] 4− ( 2 4− ), with PT=2.9×10 9 M −1 s −1 . In both cases rate enhancement in PT1 is promoted by the many Co−Co bonds on the surface of the MCC that serve as PT sites: a statistical enhancement of rate akin to the effects of proton relays. In contrast, k PT2 varies and is five orders of magnitude slower for 1 2− compared with 2 4− . Thus, MCC's and nanomaterials offer an opportunity to enhance the rate for PT1 while maintaining thermochemical or kinetic control of PT2.

Pattanayak, Santanu↗

DOE OSTI2020

Non-Equilibrium Synthesis of Highly Active Nanostructured, Oxygen-Incorporated Amorphous Molybdenum Sulfide HER Electrocatalyst

Molybdenum sulfide emerged as promising hydrogen evolution reaction (HER) electrocatalyst thanks to its high intrinsic activity, however its limited active sites exposure and low conductivity hamper its performance. To address these drawbacks, the non-equilibrium nature of pulsed laser deposition (PLD) is exploited to synthesize self-supported hierarchical nanoarchitectures by gas phase nucleation and sequential attachment of defective molybdenum sulfide clusters. Furthermore, the physics of the process are studied by in situ diagnostics and correlated to the properties of the resulting electrocatalyst. The as-synthesized architectures have a disordered nanocrystalline structure, with nanodomains of bent, defective S-Mo-S layers embedded in an amorphous matrix, with excess sulfur and segregated molybdenum particles. Oxygen incorporation in this structure fosters the creation of amorphous oxide/oxysulfide nanophases with high electrical conductivity, enabling fast electron transfer to the active sites. The combined effect of the nanocrystalline pristine structure and the surface oxidation enhances the performance leading to small overpotentials, very fast kinetics (35.1 mV dec -1 Tafel slope) and remarkable long-term stability for continuous operation up to -1 A cm -2 . This work shows possible new avenues in catalytic design arising from a non-equilibrium technique as PLD and the importance of structural and chemical control to improve the HER performance of MoS-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Electrolyte-Induced Restructuring of Acid-Stable Oxygen Evolution Catalysts

Crystalline metal oxide catalysts operating under oxygen evolution reaction (OER) conditions invariably restructure, resulting in active sites with hydroxo/oxo species in an amorphous environment. An increase in the population of terminal hydroxo/oxo species (i.e., edge sites) facilitates proton-coupled electron-transfer (PCET) kinetics for oxygen generation and thus improves catalyst competency. While amorphous films benefit from a greater density of active sites, they suffer from diminished charge transport as compared to that of extended crystalline lattices. Managing this amorphous–crystalline dichotomy is essential when designing OER catalysts, which we highlight with the examination of electrodeposited PbO x materials, which historically are very poor OER catalysts. Along these lines, the presence of phosphate during PbO x electrodeposition truncates the growth of an extended lattice owing to its strong bonding to oxide surfaces to afford an amorphous catalyst film (A-PbO x ) with significant charge-transfer resistance (138 ± 42 Ω) and poor OER kinetics (420 ± 105 mV dec –1 Tafel slope). Conversely, electrodeposition of Pb 2+ in the presence of less coordinating electrolytes such as nitrate affords crystalline β-PbO2 with improved charge-transfer resistance (42.6 ± 1.1 Ω), though still poor OER kinetics (134 ± 36 mV dec –1 Tafel slope). By operating amorphous A-PbOx in less coordinating electrolytes, however, a new partially crystalline material can be generated (μc-PbO x ) with further reduced charge-transfer resistance (33.0 ± 1.4 Ω) and improved OER kinetics (70 ± 15 mV dec –1 Tafel slope). The enhanced OER activity of μc-PbO x is the result of coupling the high edge-site population of an amorphous PbOx phase with crystalline-like charge transport properties. Finally, the ability to use an electrolyte to induce OER activity in an inactive amorphous form of PbO x highlights the benefits of optimizing the amorphous–crystalline phase compositions in the design of active OER catalysts.

catalysts↗

DOE OSTI2025

Bridging the Gap in Carbon Free Iron Making: How Hydrogen Affects the Reduction of Iron Ore between 900 and 1590 °C

Hydrogen-based reduction of iron ore for iron and steel production has emerged as a promising alternative to coal and natural gas. Unlike other hydrogen-based iron ore reduction studies, this research focuses on a wide temperature range across 900–1590 °C, encompassing reduction in solid, mixed, and liquid (slag) phases. For a 20 min exposure to hydrogen, the reduction degree increased monotonically from ∼35% at 900 °C to >90% at 1550 °C, except between 1100 °C and 1400 °C, where it stagnated ∼60%. This experimental work challenges the widely accepted notion that higher temperatures enhance the reduction process. Instead, it reveals an overlooked kinetic bottleneck, suggesting complex thermodynamic and mass transfer limitations influenced by phase transformations, diffusion barriers, and microstructural changes. Density functional theory-based molecular dynamics simulations indicate that oxygen diffusivity in BCC iron is 3.88 × 10 –5 cm 2 /s which is ∼5–10 times higher than that in FCC iron. This study reports that this stagnant reduction degree in the mixed solid–liquid phase is due to competition of multiple mechanisms, such as surface- and bulk-diffusion, pore collapse mechanisms, and crystallographic transitions.

08 HYDROGEN↗

DOE OSTI2024

Twisto-Electrochemical Activity Volcanoes in Trilayer Graphene

In this work, we develop a twist-dependent electrochemical activity map, combining a low-energy continuum electronic structure model with modified Marcus–Hush–Chidsey kinetics in trilayer graphene. We identify a counterintuitive rate enhancement region spanning the magic angle curve and incommensurate twists in the system geometry. We find a broad activity peak with a ruthenium hexamine redox couple in regions corresponding to both magic angles and incommensurate angles, a result qualitatively distinct from the twisted bilayer case. Flat bands and incommensurability offer new avenues for reaction rate enhancements in electrochemical transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Tunable angle-dependent electrochemistry at twisted bilayer graphene with moiré flat bands

Tailoring electron transfer dynamics across solid–liquid interfaces is fundamental to the interconversion of electrical and chemical energy. Stacking atomically thin layers with a small azimuthal misorientation to produce moiré superlattices enables the controlled engineering of electronic band structures and the formation of extremely flat electronic bands. Here, we report a strong twist-angle dependence of heterogeneous charge transfer kinetics at twisted bilayer graphene electrodes with the greatest enhancement observed near the ‘magic angle’ (~1.1°). Furthermore, this effect is driven by the angle-dependent tuning of moiré-derived flat bands that modulate electron transfer processes with the solution-phase redox couple. Combined experimental and computational analysis reveals that the variation in electrochemical activity with moiré angle is controlled by a structural relaxation of the moiré superlattice at twist angles of <2°, and ‘topological defect’ AA stacking regions, where flat bands are localized, produce a large anomalous local electrochemical enhancement that cannot be accounted for by the elevated local density of states alone.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Three-dimensional flat bands in pyrochlore metal CaNi 2

Electronic flat-band materials host quantum states characterized by a quenched kinetic energy. These flat bands are often conducive to enhanced electron correlation effects and emergent quantum phases of matter. Long studied in theoretical models, these systems have received renewed interest after their experimental realization in van der Waals heterostructures and quasi-two-dimensional (2D) crystalline materials. An outstanding experimental question is if such flat bands can be realized in three-dimensional (3D) networks, potentially enabling new materials platforms and phenomena. Here we investigate the C15 Laves phase metal CaNi 2 , which contains a nickel pyrochlore lattice predicted at a model network level to host a doubly-degenerate, topological flat band arising from 3D destructive interference of electronic hopping. Using angle-resolved photoemission spectroscopy, we observe a band with vanishing dispersion across the full 3D Brillouin zone that we identify with the pyrochlore flat band as well as two additional flat bands that we show arise from multi-orbital interference of Ni d -electrons. Furthermore, we demonstrate chemical tuning of the flat-band manifold to the Fermi level that coincides with enhanced electronic correlations and the appearance of superconductivity. Extending the notion of intrinsic band flatness from 2D to 3D, this provides a potential pathway to correlated behaviour predicted for higher-dimensional flat-band systems ranging from tunable topological to fractionalized phases.

36 MATERIALS SCIENCE↗

NASA NTRS1974

Observations of coronal disturbances from 1 to 9 solar radii. I - First event of 1973 January 11

H alpha, white-light and radio observations of a coronal disturbance on Jan. 11, 1973, commencing at about 0036 hr UT show that a piston-driven shock wave propagated outward through the corona to heights of at least 9 solar radii. Probably most of the expelled coronal gas originated in a coronal enhancement in the lower corona. An estimate of the kinetic energy and the mass of the expelled gas is obtained which is compatible with observations of piston-driven shock waves near the earth. Shock-wave parameters are evaluated, and a model of the disturbance is outlined.

Stewart, R. T.↗

NASA NTRS1981

Effects of truncation in modal representations of thermal convection

The Galerkin equations for convection in a sphere are examined to determine which physical processes are neglected by the severe truncation of the equations of motion. It is demonstrated that the gross features of the flow are affected by truncation in the horizontal direction, with all of the models considered being well resolved in the vertical direction. One of the effects of truncation is to enhance the high-wave number end of the kinetic energy and thermal variance spectra. The examples cited indicate that as long as the kinetic energy spectrum decreases with wave number, a truncation gives a qualitatively correct solution. Conclusions are tested by calculating solutions to the equations of motion for several values of the Rayleigh number and the limit of horizontal spatial resolution.

Marcus, P. S.↗

NASA NTRS1991

Atmospheric turbulence review of space shuttle launches

Research and analysis on the identification of turbulent regions from the surface to 16 km during Space Shuttle launches are discussed. It was demonstrated that the results from the FPS-16 radar/jimsphere balloon system in measuring winds can indeed indicate the presence or conditions ripe for turbulence in the troposphere and lower stratosphere. It was further demonstrated that atmospheric data obtained during the shuttle launches by the rawinsonde in conjunction with the jimsphere provides the necessary meteorological data to compute aerodynamic parameters to identify turbulence, such as Reynolds number drag coefficient, turbulent stresses, total energy, stability parameter, vertical gradient of kinetic energy, Richardson number, and the turbulence probability index. Enhanced temperature lapse rates and inversion rates, strong vector wind shears, and large changes in wind direction identify the occurrence of turbulence at the troposphere. When any two of the above conditions occur simultaneously, a significant probability of turbulence can occur.

Susko, Michael↗

NASA NTRS1994

Loop heating by D.C. electric current and electromagnetic wave emissions simulated by 3-D EM particle zone

We have shown that a current-carrying plasma loop can be heated by magnetic pinch driven by the pressure imbalance between inside and outside the loop, using a 3-dimensional electromagnetic (EM) particle code. Both electrons and ions in the loop can be heated in the direction perpendicular to the ambient magnetic field, therefore the perpendicular temperature can be increased about 10 times compared with the parallel temperature. This temperature anisotropy produced by the magnetic pinch heating can induce a plasma instability, by which high-frequency electromagnetic waves can be excited. The plasma current which is enhanced by the magnetic pinch can also excite a kinetic kink instability, which can heat ions perpendicular to the magnetic field. The heating mechanism of ions as well as the electromagnetic emission could be important for an understanding of the coronal loop heating and the electromagnetic wave emissions from active coronal regions.

Sakai, J. I.↗

NASA NTRS2003

Quantitative Studies on the Propagation and Extinction of Near-Limit Premixed Flames Under Normal and Microgravity

The main objective of this research is to introduce accurate fluid mechanics measurements diagnostics in the 2.2-s drop tower for the determination of the detailed flow-field at the states of extinction. These results are important as they can then be compared with confidence with detailed numerical simulations so that important insight is provided into near-limit phenomena that are controlled by not well-understood kinetics and thermal radiation processes. Past qualitative studies did enhance our general understanding on the subject. However, quantitative studies are essential for the validation of existing models that subsequently be used to describe near-limit phenomena that can initiate catastrophic events in micro- and/or reduced gravity environments.

Dong, Y.↗

DOE OSTI2025

Development for Integrated System-Level Analysis Capabilities in SAM for Molten Salt Reactors

In recent years, there has been renewed interest in Molten Salt Reactors (MSRs) for their potential advantages compared to reactors that rely on solid fuel. In response to such interest, many methods and codes have been developed to capture the unique features of MSRs. Among them, the System Analysis Module (SAM) is a modern system analysis tool that provides fast-running, modest-fidelity, whole-plant transient analysis capabilities, essential for fast-turnaround design scoping and engineering analyses of advanced reactor concepts. For liquid-fuel MSRs, the complex physics and chemistry involved in MSR operation—such as reactor kinetics, fluid flow, heat transfer, and salt composition dynamics—pose significant challenges for system-level modeling. Specific modeling capabilities are needed for system-level transient simulation. This paper presents recent advancements in SAM capability enhancements for system-level modeling of MSRs, focusing on improved simulation fidelity, computational efficiency, and multi-physics integration. Key enhancements include the development of species transport, Delayed Neutron Precursor (DNP) drift, modified Point Kinetics Equations (PKE), decay heat modeling, key fission product behavior, salt corrosion, and thermal-hydraulic coupling, as well as code robustness and performance enhancements for MSR applications. The code enhancement allows for better predictive accuracy in safety analysis, transient behavior, and operational optimization, thus supporting the design and licensing of next-generation MSRs. Results from case studies are presented to demonstrate the benefits of these enhancements in accurately capturing key reactor transient behaviors.

Hu, Rui (ORCID:0000000237712920)↗

DOE OSTI2026

Enhancing Oxygen Evolution Reaction and Stability in Proton-Conducting Solid Oxide Electrolysis Cells (p-SOECs) via a Porous Gadolinium-Doped Ceria Interlayer

Proton-conducting solid oxide electrolysis cells (p-SOECs) offer a promising pathway for intermediate temperature (400-600 °C) hydrogen production. However, they still face critical challenges related to sluggish oxygen evolution reaction (OER) kinetics and low Faradaic efficiencies. Here, in this work, we demonstrate that introducing a thin (~0.8 µm) porous Gd 0.1 Ce 0.9 O 1.95 (GDC) interlayer between a BaCo 0.8 Zr 0.1 Zn 0.1 O 3-δ (BCZZ) oxygen electrode and electrolyte significantly enhances p-SOEC performance. The GDC interlayer reduces polarization resistance by 48% (0.54 to 0.28 O cm 2 ) and increases Faradaic efficiency from 63% to 81% at -0.8 A/cm 2 and 600 °C. GDC interlayer p-SOECs display elevated effective H 2 current densities compared to control p-SOECs and reach up to -1.22 A/cm 2 at 1.3 V. Mechanistic studies on the interactions between GDC and BCZZ reveal that GDC intrinsically promotes OER kinetics by significantly reducing the polarization activation energy (Ea p ), dropping from 1.45 to 1.22 eV for full p-SOECs and 0.98 to 0.76 eV for symmetric cells. This promotional effect is localized in the electrochemically active region near the electrolyte interface. Durability testing for over 1500 hours under 50% H 2 O conditions indicates that the GDC interlayer also improves long-term stability, with a degradation rate 53% lower than control p-SOECs. By pinpointing the interfacial region where GDC exerts its promotional effect, highlighting its role in enhancing OER kinetics, and establishing interlayer engineering as a powerful technique, this work provides a unified pathway to simultaneously improve p-SOEC activity, Faradaic efficiency, and durability.

08 - HYDROGEN↗

DOE OSTI2020

Cross-field electron diffusion due to the coupling of drift-driven microinstabilities

In this paper, the nonlinear interaction between kinetic instabilities driven by multiple ion beams and magnetized electrons is investigated. Electron diffusion across magnetic field lines is enhanced by the coupling of plasma instabilities. Here, a two-dimensional collisionless particle-in-cell simulation is performed accounting for singly and doubly charged ions in a cross-field configuration. Consistent with prior linear kinetic theory analysis and observations from coherent Thomson scattering experiments, the present simulations identify an ion-ion two-stream instability due to multiply charged ions (flowing in the direction parallel to the applied electric field) which coexists with the electron cyclotron drift instability (propagating perpendicular to the applied electric field and parallel to the ExB drift). Small-scale fluctuations due to the coupling of these naturally driven kinetic modes are found to be a mechanism that can enhance cross-field electron transport and contribute to the broadening of the ion velocity distribution functions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Unraveling the Pyrolytic Behavior and Kinetics of Single Polymers and Plastic-Rich Municipal Solid Waste Using Thermal Analysis

Pyrolysis is a highly promising thermochemical recycling technology for converting heterogenous plastic waste into sustainable fuels in a single step. Therefore, understanding the pyrolysis mechanism is essential for enabling rational reactor design and enhancing efficient recycling techniques. In this study, the thermal degradation behaviors and corresponding kinetics of pure polymers (PE, PP, and PET) and plastic-rich MSW were examined using simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Experiments were carried out in the temperature range of 30-800°C with variable heating rates from 5°C/min to 20°C/min in an ultra-high purity Argon atmosphere. Our results indicated that the plastic pyrolysis was an endothermic process, with varying decomposition temperature ranges depending on their structure and composition. Various iso-conversional model-free methods (Friedman, Flynn-Wall-Ozawa, Starink, and Kissinger-Akahira-Sunose) were utilized to determine the apparent activation energy of the plastic degradation, which increased in the following order: PET (214 kJ/mol), PP (218 kJ/mol), PE (245 kJ/mol), and MSW (249 kJ/mol). Finally, Criado’s master plots were employed to identify the best-fitting reaction model and the pre-exponential factor was subsequently determined.

Bashir, Muhammad Aamir↗

NASA NTRS1990

Production of oxygen from lunar ilmenite

The following subjects are addressed: (1) the mechanism and kinetics of carbothermal reduction of simulated lunar ilmenite using carbon and, particularly, CO as reducing agents; (2) the determination of the rate-limiting steps; (3) the investigation of the effect of impurities, particularly magnesium; (4) the search for catalysts suitable for enhancement of the rate-limiting step; (5) the comparison of the kinetics of carbothermal reduction with those of hydrogen reduction; (6) the study of the combined use of CO and hydrogen as products of gasification of carbonaceous solids; (7) the development of reduction methods based on the use of waste carbonaceous compounds for the process; (8) the development of a carbothermal reaction path that utilizes gasification of carbonaceous solids to reducing gaseous species (hydrocarbons and carbon monoxide) to facilitate the reduction reaction kinetics and make the process more flexible in using various forms of carbonaceous feeds; (9) the development of advanced gas separation techniques, including the use of high-temperature ceramic membranes; (10) the development of an optimum process flow sheet for carbothermal reduction, and comparison of this process with the hydrogen reduction scheme, as well as a general comparison with other leading oxygen production schemes; and (11) the use of new and advanced material processing and separation techniques.

Zhao, Y.↗

DOE OSTI2021

Atomistic modeling of meso -timescale processes with $\mathrm{SEAKMC}$: A perspective and recent developments

On-the-fly kinetic Monte Carlo (kMC) methods have recently garnered significant attentions after successful applications to various atomic-scale problems using a timescale outside the reach of classical molecular dynamics. These methods play a critical role in modeling atomistic meso-timescale processes, and it is therefore essential to further improve their capabilities. In this report we review one of the on-the-fly kMC methods, Self-Evolving Atomistic kinetic Monte Carlo (SEAKMC) and propose two schemes that considerably enhance the efficiency of saddle point searches (SPSs) during the simulations. The performance of these schemes is tested using the diffusion of point defects in bcc Fe. In addition, we discuss approaches to significantly mitigate limitations of these schemes, which further improves their efficiencies. Importantly, these schemes improve the SPS efficiency not only for SEAKMC but also for other on-the-fly kMC methods, broadening the applications of on-the-fly kMC simulations to complex meso-timescale problems.

36 MATERIALS SCIENCE↗