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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Studies of Helium Behavior in Uranium Hexafluoride

Several issues have arisen from experimental observations and/or theoretical postulation related to the behavior of helium in uranium hexafluoride (UF 6 ) matrices and how it may impact the ability to use this noble gas to quantify the fill date of the cylinder. A series of experiments was conducted to address several such issues, and the results and implications are reported here. Two issues relate to bias in the helium measurement due to ambient air from extraneous sources such as atmospheric air or from potential holdup in a large, activated alumina chemical trap. These issues are really a question of differential retention of helium versus three other inert gas isotopes (representative of other noble gases found in air) used as a calibration for air in leakage. Discernable bias was not detected in either case. Another issue had to do with helium potentially brought into the cylinder by a liquid UF 6 fill and subsequently released as the material solidifies and/or during storage. The solubility of helium in liquid UF 6 was measured to investigate this theory. The experiment quantified the potential magnitude of the initial helium contribution if present. The final issue was that of retention of helium in solid UF 6 . Investigation of this theory necessitated quantifying both the solubility and the diffusivity of helium in UF 6 . In one experiment, the solubility was measured at cryogenic temperature, allowing quantification of helium in solid UF 6 such as would be found in a cold trap. In a second experiment, transport of helium into and through a macroscopic plug of solid UF 6 was examined. The transport was very slight although apparently detectible. Effectively, only an upper limit to the transport could be determined, but that limit implied that helium holdup in solid UF 6 is a real possibility.

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

Cubic-meter scale laboratory fault re-activation experiments to improve the understanding of induced seismicity risks

Abstract To understand fluid induced seismicity, we have designed a large-scale laboratory experiment consisting of a one-cubic-meter sandstone with an artificial fault cut and fluid-injection boreholes. The sandstone block is assembled in a true triaxial loading frame and equipped with 38 piezoelectric sensors to locate and characterise acoustic emission events. The differential stress on the artificial fault is increased in stages to bring it towards a critically stressed state. After each stage of differential stress increase, fluids are injected at low pressures through boreholes to test the potential of fault re-activation. In addition, a high-pressure injection was conducted that created a hydraulic fracture from the injection borehole towards the artificial fault. The newly generated fluid pathway resulted in an activation of the complete block through a stick–slip movement. We compare acoustic emission measurements from the laboratory experiment with seismicity observations from the field-scale CO 2 injection at Decatur, Illinois, U.S., and conclude that the existence of fluid pathways plays a decisive role for the potential of induced seismicity.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Identification of Active Sites of Pure and Nitrogen-Doped Carbon Materials for Oxygen Reduction Reaction Using Constant-Potential Calculations

Nitrogen-doped carbon materials are promising metal-free catalysts for the electrochemical oxygen reduction reaction (ORR). A better theoretical understanding on the nature of the active site(s) would help further optimization of their ORR activity. Although quantum mechanical calculations have been widely employed to elucidate the active sites over various catalysts, these calculations are typically done assuming constantcharge conditions rather than the experimentally relevant constant-potential conditions. In this study, we employ the double-reference method to simulate the energetics of the ORR over pure and N-doped carbon materials under constant-potential conditions. We demonstrate that constant-potential calculations enable more accurate theoretical predictions, comparing well with existing experiments. Our key findings are (1) the zigzag edge of pure graphite is highly active for ORR, (2) the pyridinic N-doped armchair edge is highly active for ORR in alkaline media but not in acid, and (3) graphitic N can donate electrons to pyridinic N to enhance the ORR activity. Furthermore, these fundamental insights provide guidelines for the design of better carbonbased ORR catalysts.

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

Conjugation effect of amine molecules in non-aqueous Mg redox flow batteries

Nonaqueous magnesium redox flow batteries (Mg RFBs) are attractive for low-cost, high-energy-density and long-cycle-life stationary energy storage applications. However, state-of-the-art cathode redox-active molecules suffer from low solubility and low redox potential. Herein, we screened a range of cathode redox-active molecules and identified amine molecules as optimal to couple with the Mg anode. The properties of amine derivatives and their performances were collected to establish the correlation between molecular structures and electrochemical performances. The redox potential and solubility of these amine molecules were influenced by the π-conjugated and non-conjugated structures of amine derivatives. Density functional theory (DFT) simulations and the inverse aromatic fluctuation index (FLU −1 ) verified that conjugation had an important role in stabilizing the molecule and increasing its redox potential. Notably, tris[4-(diethylamino)phenyl]amine (TDPA) achieved the highest theoretical energy density (∼120 Wh L −1 ) due to its high solubility (∼0.9 M) and voltage (∼2.5 V vs. Mg/Mg 2+ ). We also demonstrated that ether solvents were crucial for stable, high-solubility catholytes, while bulk anions did not affect the redox potential of these p-type molecules. In a Mg-amine RFB configuration, the battery delivered 2.50 V, a specific discharge capacity of 106.5 mAh g −1 , an initial coulombic efficiency of 90.74%, and a capacity retention of 93.88% after 150 cycles.

Qin, Yunan [University of Utah, Salt Lake City, UT↗
DOE OSTI2022

Rnf and Fix Have Specific Roles during Aerobic Nitrogen Fixation in Azotobacter vinelandii

Biological nitrogen fixation requires large amounts of energy in the form of ATP and low potential electrons to overcome the high activation barrier for cleavage of the dinitrogen triple bond. The model aerobic nitrogen-fixing bacteria, Azotobacter vinelandii, generates low potential electrons in the form of reduced ferredoxin (Fd) and flavodoxin (Fld) using two distinct mechanisms via the enzyme complexes Rnf and Fix. Both Rnf and Fix are expressed during nitrogen fixation, but deleting either rnf1 or fix genes has little effect on diazotrophic growth. However, deleting both rnf1 and fix eliminates the ability to grow diazotrophically. Rnf and Fix both use NADH as a source of electrons, but overcoming the energetics of NADH's endergonic reduction of Fd/Fld is accomplished through different mechanisms. Rnf harnesses free energy from the chemiosmotic potential, whereas Fix uses electron bifurcation to effectively couple the endergonic reduction of Fd/Fld to the exergonic reduction of quinone. Different reaction stoichiometries and condition-specific differential gene expression indicate specific roles for the two reactions. This work's complementary physiological studies and thermodynamic modeling reveal how Rnf and Fix balance redox homeostasis in various conditions. Specifically, the Fix complex is required for efficient growth under low oxygen concentrations, while Rnf is presumed to maintain reduced Fd/Fld production for nitrogenase under standard conditions. This work provides a framework for understanding how the production of low potential electrons sustains robust nitrogen fixation in various conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Effects of open circuit immersion and vertex potential on potentiodynamic polarization scans of metallic biomaterials

Abstract Electrodes made of commercially pure titanium (CP-Ti) and a CoCrMo alloy are immersed at an open circuit in a phosphate buffer saline electrolyte at room temperature for different durations prior to electrochemical analyses. Open circuit potential measurements, electrochemical impedance spectroscopy measurements, and cyclic potentiodynamic polarization (CPP) scans are used to assess the impact of the immersion time on derived property values. Stable passivation layers formed on both materials during immersion. The corrosion potentials determined from the anodic legs of CPP scans become more cathodic, and the corrosion currents decrease to lower values after longer immersion times. Measured currents indicate the layers formed on CP-Ti stabilize during forward anodic scans and persist to the vertex potential, whereas passivation breakdown occurs during anodic scans with CoCrMo with active corrosion at voltages up to the vertex potential. The characteristics of the return cathodic legs of CPP scans represent the surface conditions at the vertex potential: characteristic corrosion property values derived from the test responses represent passive surfaces on CP-Ti and leached surfaces on CoCrMo rather than intrinsic properties of those materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Resolving Issues Regarding Disposal of Safeguarded Nuclear Materials: Concepts for Near Surface and Intermediate Depth Disposal sites

This document presents two case studies on nuclear waste disposal to explore the safeguards challenges and potential solutions present under each scenario. Both involve the disposal of nuclear materials, either for waste containing safeguarded nuclear materials or waste where safeguards on the nuclear materials have been previously terminated. The first case study is that of a low-level waste (LLW) repository that is situated near the surface. This facility will accept safeguarded nuclear materials for disposal. Examples of this type of activity are rare, but the potential for more facilities of this type is very possible as States become more comfortable with considering safeguards measures in perpetuity on deep geological repositories. The second study extends this to the case of terminated wastes at an intermediate depth disposal site. In this case, the reasons why terminated nuclear materials could be found in these disposal facilities and how obligations under the Comprehensive Safeguards Agreement (CSA) and Additional Protocol (AP) are met when the disposed waste items are intermediate level waste (ILW) or high-level waste (HLW).

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2023

A computational study of how surfaces affect slip family activity

Plastic deformation behavior is most conveniently assessed by characterization on a surface, but whether such observations are representative of bulk properties is uncertain. Motivated by reported inconsistencies in slip resistance probed at different depths, we investigated (i) whether the average slip family activity is affected by the presence of a surface and (ii) how the kinematic nature of available slip families influences a potential surface effect. The slip family activity as a function of distance from the surface was extracted from full-field crystal plasticity simulations of random polycrystalline hexagonal close-packed (HCP) and body-centered cubic (BCC) metals as examples of mixed in contrast to universally-high numbers of slip systems per family. Under certain conditions, a deviation from bulk slip activity is observed up to about two grains from the surface. For the easiest (least slip-resistant) family, a surface effect of decreasing activity with depth emerges if the number of slip systems falls below about six. For harder families, slip activity always increases with depth. Furthermore, these phenomena are explained on the basis of varying constraints with depth in connection with the kinematic properties of slip families in the material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Direct coherent switching with decay of mixing for intersystem crossing dynamics of thioformaldehyde: The effect of decoherence

We evaluate the effect of electronic decoherence on intersystem crossing in the photodynamics of thioformaldehyde. First, we show that the state-averaged complete-active-space self-consistent field electronic structure calculations with a properly chosen active space of 12 active electrons in 10 active orbitals can predict the potential energy surfaces and the singlet–triplet spin–orbit couplings quite well for CH 2 S, and we use this method for direct dynamics by coherent switching with decay of mixing (CSDM). We obtain similar dynamical results with CSDM or by adding energy-based decoherence to trajectory surface hopping, with the population of triplet states tending to a small steady-state value over 500 fs. Without decoherence, the state populations calculated by the conventional trajectory surface hopping method or the semiclassical Ehrenfest method gradually increase. This difference shows that decoherence changes the nature of the results not just quantitatively but qualitatively.

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

Seasonal Fluctuations in Iron Cycling in Thawing Permafrost Peatlands

In permafrost peatlands, up to 20% of total organic carbon (OC) is bound to reactive iron (Fe) minerals in the active layer overlying intact permafrost, potentially protecting OC from microbial degradation and transformation into greenhouse gases (GHG) such as CO 2 and CH 4 . During the summer, shifts in runoff and soil moisture influence redox conditions and therefore the balance of Fe oxidation and reduction. Whether reactive iron minerals could act as a stable sink for carbon or whether they are continuously dissolved and reprecipitated during redox shifts remains unknown. We deployed bags of synthetic ferrihydrite (FH)-coated sand in the active layer along a permafrost thaw gradient in Stordalen mire (Abisko, Sweden) over the summer (June to September) to capture changes in redox conditions and quantify the formation and dissolution of reactive Fe(III) (oxyhydr)oxides. We found that the bags accumulated Fe(III) under constant oxic conditions in areas overlying intact permafrost over the full summer season. In contrast, in fully thawed areas, conditions were continuously anoxic, and by late summer, 50.4 ± 12.8% of the original Fe(III) (oxyhydr)oxides were lost via dissolution. Periodic redox shifts (from 0 to +300 mV) were observed over the summer season in the partially thawed areas. This resulted in the dissolution and loss of 47.2 ± 20.3% of initial Fe(III) (oxyhydr)oxides when conditions are wetter and more reduced, and new formation of Fe(III) minerals (33.7 ± 8.6% gain in comparison to initial Fe) in the late summer under more dry and oxic conditions, which also led to the sequestration of Fe-bound organic carbon. Our data suggest that there is seasonal turnover of iron minerals in partially thawed permafrost peatlands, but that a fraction of the Fe pool remains stable even under continuously anoxic conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Mitigation of backgrounds from cosmogenic 137 Xe in xenon gas experiments using 3 He neutron capture

136 Xe is used as the target medium for many experiments searching for 0νββ. Despite underground operation, cosmic muons that reach the laboratory can produce spallation neutrons causing activation of detector materials. A potential background that is difficult to veto using muon tagging comes in the form of 137 Xe created by the capture of neutrons on 136 Xe. This isotope decays via beta decay with a half-life of 3.8 minutes and a Q β of ~4.16 MeV. This work proposes and explores the concept of adding a small percentage of 3 He to xenon as a means to capture thermal neutrons and reduce the number of activations in the detector volume. When using this technique we find the contamination from 137 Xe activation can be reduced to negligible levels in tonne and multi-tonne scale high pressure gas xenon neutrinoless double beta decay experiments running at any depth in an underground laboratory.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Mitigation of Backgrounds from Cosmogenic $^{137}$Xe in Xenon Gas Experiments using $^{3}$He Neutron Capture

\Xe{136} is used as the target medium for many experiments searching for \bbnonu. Despite underground operation, cosmic muons that reach the laboratory can produce spallation neutrons causing activation of detector materials. A potential background that is difficult to veto using muon tagging comes in the form of \Xe{137} created by the capture of neutrons on \Xe{136}. This isotope decays via beta decay with a half-life of 3.8 minutes and a \Qb\ of $\sim$4.16 MeV. This work proposes and explores the concept of adding a small percentage of \He{3} to xenon as a means to capture thermal neutrons and reduce the number of activations in the detector volume. When using this technique we find the contamination from \Xe{137} activation can be reduced to negligible levels in tonne and multi-tonne scale high pressure gas xenon neutrinoless double beta decay experiments running at any depth in an underground laboratory.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Cu[Ni(2,3-pyrazinedithiolate) 2 ] Metal–Organic Framework for Electrocatalytic Hydrogen Evolution

The application of metal–organic frameworks (MOFs) as electrocatalysts for small molecule activation has been an emerging topic of research. Previous studies have suggested that two-dimensional (2D) dithiolene-based MOFs are among the most active for the hydrogen evolution reaction (HER). Here, a three-dimensional (3D) dithiolene-based MOF, Cu[Ni(2,3-pyrazinedithiolate) 2 ] (1), is evaluated as an electrocatalyst for the HER. In pH 1.3 aqueous electrolyte solution, 1 exhibits a catalytic onset at –0.43 V vs the reversible hydrogen electrode (RHE), an overpotential (η 10 mA/cm 2 ) of 0.53 V to reach a current density of 10 mA/cm 2 , and a Tafel slope of 69.0 mV/dec. Interestingly, under controlled potential electrolysis, 1 undergoes an activation process that results in a more active catalyst with a 200 mV reduction in the catalytic onset and η 10 mA/cm 2 . It is proposed that the activation process is a result of the cleavage of Cu–N bonds in the presence of protons and electrons. Furthermore, this hypothesis is supported by various experimental studies and density functional theory calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Propane Dehydrogenation Catalyzed by Supported Group IV (Ti, Zr, Hf) Organometallics on Silicon Nitride

Mesoporous silicon nitride (Si 3 N 4 ) enables access to chemisorbed group IV organometallics catalysts active for propane dehydrogenation (PDH) compared to the organometallic analogues on mesoporous silica under the same reaction conditions. The series of Si 3 N 4 -supported materials are active catalysts, (Zr > Hf > Ti k f = 290, 232, and 162 mol mol Metal -1 h -1 at 450 °C with 2% C 3 H 8 in Ar, respectively) with selectivity above 95%, demonstrating additional examples of Ti and Hf systems for PDH. However, the underlying mechanism of the improved performance relative to oxide supported homologues is not well-understood. Characterization of thermally treated samples (DRIFTS, XAS and SSNMR) and computational modeling of this catalyst series was utilized to differentiate between potential amido - (C-H activation along the M-N bond) and imido - (C-H activation along the M=N bond) mechanisms. Due to remaining mechanistic ambiguity, a Ga analogue was synthesized and evaluated for PDH activity as an indirect probe to experimentally differentiate pathways. An inversion of the oxide/nitride performance trend is observed for the Ga congener which does not form a Ga=N bond, most consistent with different mechanisms dictating the performance of the group IV/Si 3 N 4 catalysts vs Ga/Si 3 N 4 .

heterolytic cleavage↗
DOE OSTI2026

Dynamic Electric Field Assisted CO 2 Methanation

Energy-efficient advanced chemical reactions are essential for accelerating the growth of hydrocarbon economy. Sabatier reaction stands out for its potential to effectively transform carbon dioxide into valuable hydrocarbons and is an asset for long-duration Mars missions. This study explores a novel catalytic approach that harnesses electric field-assisted catalysis to substantially enhance the efficiency of the Sabatier reaction. Application of a dynamically perturbed electric field at 1000 Hz resulted in remarkable enhancements, increasing methane formation rates by over 100% at 350 °C and by 74% at 400 °C. Post-reaction catalyst characterization further revealed reduced blockage of active catalytic surface area under the applied electric field, emphasizing improved catalytic longevity and sustained activity. These results underscore the potential of tailored electric field waveforms to dynamically modulate elementary reaction kinetics and surface processes, positioning electric field-assisted catalysis as a transformative strategy for energy-efficient, cost-effective chemical manufacturing and energy conversion technologies.

42 - ENGINEERING↗
DOE OSTI2022

Platinum Graphene Catalytic Condenser for Millisecond Programmable Metal Surfaces

Accelerating catalytic chemistry and tuning surface reactions require precise control of the electron density of metal atoms. In this work, nanoclusters of platinum were supported on a graphene sheet within a catalytic condenser device that facilitated electron or hole accumulation in the platinum active sites with negative or positive applied potential, respectively. The catalytic condenser was fabricated by depositing on top of a p-type Si wafer an amorphous HfO 2 dielectric (70 nm), on which was placed the active layer of 2–4 nm platinum nanoclusters on graphene. A potential of ±6 V applied to the Pt/graphene layer relative to the silicon electrode moved electrons into or out of the active sites of Pt, attaining charge densities more than 1% of an electron or hole per surface Pt atom. At a level of charge condensation of ±10% of an electron per surface atom, the binding energy of carbon monoxide to a Pt(111) surface was computed via density functional theory to change 24 kJ mol –1 (0.25 eV), which was consistent with the range of carbon monoxide binding energies determined from temperature-programmed desorption (ΔBE CO of 20 ± 1 kJ mol –1 or 0.19 eV) and equilibrium surface coverage measurements (ΔBE CO of 14 ± 1 kJ mol –1 or 0.14 eV). Impedance spectroscopy indicated that Pt/graphene condensers with potentials oscillating at 3000 Hz exhibited negligible loss in capacitance and charge accumulation, enabling programmable surface conditions at amplitudes and frequencies necessary to achieve catalytic resonance.

Inorganic carbon compounds↗
DOE OSTI2023

Site Diversity and Mechanism of Metal–Exchanged Zeolite Catalyzed Non–Oxidative Propane Dehydrogenation

Metal-exchanged zeolites are well-known propane dehydrogenation (PDH) catalysts; however, the structure of the active species remains unresolved. In this review, existing PDH catalysts are first surveyed, and then the current understanding of metal-exchanged zeolite catalysts is described in detail. The case of Ga/H-ZSM-5 is employed to showcase that advances in the understanding of structure–activity relations are often accompanied by technological or conceptional breakthroughs. The understanding of Ga speciation at PDH conditions has evolved owing to the advent of in situ/operando characterizations and to the realization that the local coordination environment of Ga species afforded by the zeolite support has a decisive impact on the active site structure. In situ/operando quantitative characterization of catalysts, rigorous determination of intrinsic reaction rates, and predictive computational modeling are all significant in identifying the most active structure in these complex systems. The reaction mechanism could be both intricately related to and nearly independent of the details of the assumed active structure, as in the two main proposed PDH mechanisms on Ga/H-ZSM-5, that is, the carbenium mechanism and the alkyl mechanism. Perspectives on potential approaches to further elucidate the active structure of metal-exchanged zeolite catalysts and reaction mechanisms are discussed in the final section.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗