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At least 325 records · Page 18

Analysis of direct and indirect noise in a next-generation aviation gas turbine combustor

A large-eddy simulation (LES) of a next-generation combustor is performed to examine effects of this combustor concepts on direct and indirect combustion noise characteristics. Direct noise is computed considering the unsteady heat release predictions while entropy fluctuations in the downstream part of the combustor are used to estimate indirect noise through the transfer function of the outlet nozzle. A low-order acoustic reconstruction technique, which utilizes the Green’s function of the configuration, is developed to compute the acoustics inside the combustor. Comparisons to experimental results are reported, showing the reasonable accuracy of the LES and combustion noise computations. The direct noise spectrum peaks at frequencies around 3 kHz because of the fast timescales associated with the chemical reactions inside the combustor. In addition, the indirect noise is dominant at low frequencies, i.e., less than 400 Hz, because of the characteristics of the entropy spectrum at the outlet nozzle. Further, compared to a conventional rich-quench-lean (RQL) combustor configuration, significant differences in the acoustics are observed, and are explained by two specific technological novelties. Firstly, the direct noise spectrum peaks at significantly higher frequencies due to the combustor’s compactness. Secondly, the entropy inhomogeneties downstream of the combustion region are an order of magnitude smaller in amplitude due to the lack of dilution with cold air. This leads to a significant reduction in the indirect noise amplitude at low frequencies, where it is the dominant source of noise. These results suggest opportunities for advanced combustion technologies to achieve substantial reductions in combustion-related noise.

42 ENGINEERING↗

Electrochemical stability and corrosion behavior of Ni-Cr alloy in molten LiCl-KCl salt

This study investigated the electrochemical properties and potential-dependent stability of Cr(II) and Ni(II) in a eutectic LiCl-KCl molten salt at 500 °C under an argon atmosphere using a three-electrode cell configuration with a glassy carbon working electrode, Ag/Ag + reference electrode, and graphite counter electrode. Cyclic voltammetry was employed to characterize the Cr(0)/Cr(II)/Cr(III) and Ni(0)/Ni(II) redox transitions, yielding diffusion coefficients of 0.50 (±0.01) × 10 −5 cm 2 s −1 for Cr(II) and 0.91 (±0.16) × 10 −5 cm 2 s −1 for Ni(II) at 500 °C. The redox stability domains of these species provided insight into the corrosion mechanisms of a Ni-Cr alloy (80–20 wt %) in LiCl-KCl salt. The measured open circuit potential of the alloy corresponded to the range of potentials where the Ni(0) and Cr(II) species are stable, indicating a preferential dissolution of Cr. Immersion testing of the alloy for 336 h confirmed significant Cr depletion (or Ni-enrichment) at the surface layer, corroborating Cr dealloying as the dominant corrosion reaction under open circuit conditions. Additionally, the application of a small anodic overpotential (0.11 V) resulted in selective Cr dissolution while a large anodic overpotential (0.25 V) resulted in co-dissolution of both Cr and Ni. Furthermore, these results demonstrate that the corrosion mechanisms of a Ni-Cr alloy in LiCl-KCl depend upon the applied potential, and thus the redox conditions of the molten salt should be carefully controlled in the design of a redox buffer to mitigate corrosion in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Efficient separation and coprecipitation for simplified cathode recycling

Hydrometallurgical recycling of spent lithium-ion batteries is among the most promising recovery approaches. The current hydrometallurgical method for battery recycling faces challenges such as complex separation and precipitation processes, and environmental concerns from the use of caustic inorganic acid and hazardous hydrogen peroxide. Our proposed modified method, namely polyol-metallurgy, uses citric acid in ethylene glycol as dual-function green solution to overcome these obstacles. This bifunctional solution leaches valuable metal ions from cathode materials (e.g., LiCoO 2 ), and then acts as chelating agents to selectively precipitate cobalt through an esterification reaction, without the need for additional precipitation agents. The leaching efficiency of cobalt and lithium reaches 99.55% and 97.65%, respectively, and more than 96% of cobalt could be directly self-precipitated and recovered. Further, the unique characteristics of the dual-function solution also avoids impurities from Al foils and PVDF/carbon black films, enabling the simple separation process. Therefore, the process can be completed in one-pot system with efficient leaching, separation and coprecipitation, making it more efficient and feasible for operation than existing alternatives.

25 ENERGY STORAGE↗

Gigaton commercial-scale carbon storage and mineralization potential in stacked Columbia River basalt reservoirs

This work presents a detailed supercritical CO 2 storage resource estimation for the stacked basalt reservoirs in the Grande Ronde Basalt of the Columbia River Basalt Group in eastern Washington and Oregon. The assessment aims to derisk the commercialization potential of geologic carbon storage in basalt by leveraging both structural and mineralization trapping of CO 2 in basalt. The structural closures formed by anticlinal ridges and synclinal valleys in Yakima Fold Belt are excellent physical traps to accommodate injected supercritical CO 2 . Rigorous hydraulic testing, well logs and simulation results from the Wallula Basalt Pilot #1 well showed the occurrence of 17 suitable permeable injection zones (up to 2,496 mD) intercalated with dense seals (~2.6E-10 mD) in the Grand Ronde Basalt. In addition, geochemical studies showed fast reactions between supercritical CO 2 and dissolved basalt minerals to form stable carbonates. In conclusion, our calculation indicates up to 40 gigatons (P90) of mineralization storage resources exist in the Grande Ronde Basalt reservoirs.

58 GEOSCIENCES↗

Competitive exchange between divalent metal ions [Cu(II), Zn(II), Ca(II)] and Hg(II) bound to thiols and natural organic matter

Mercuric Hg(II) ion forms exceptionally strong complexes with various organic ligands, particularly thiols and dissolved organic matter (DOM) in natural water. Few studies, however, have experimentally determined whether or not the presence of base cations and transition metal ions, such as Ca(II), Cu(II), and Zn(II), would compete with Hg(II) bound to these ligands, as concentrations of these metal ions are usually orders of magnitude higher than Hg(II) in aquatic systems. Different from previous model predictions, a significant fraction of Hg(II) bound to cysteine (CYS), glutathione (GSH), or DOM was found to be competitively exchanged by Cu(II), but not by Zn(II) or Ca(II). About 20–75% of CYS-bound-Hg(II) [at 2:1 CYS:Hg(II)] and 14–40% of GSH-bound-Hg(II) [at 1:1 GSH:Hg(II)] were exchanged by Cu(II) at concentrations 1–3 orders of magnitude greater than Hg(II). Competitive exchange was also observed between Cu(II) and Hg(II) bound to DOM, albeit to a lower extent, depending on relative abundances of thiol and carboxylate functional groups on DOM and their equilibrium time with Hg(II). When complexed with ethylenediaminetetraacetate (EDTA), most Hg(II) could be exchanged by Cu(II) and Zn(II), as well as Ca(II) at increasing concentrations. Furthermore, these results shed additional light on competitive exchange reactions between Hg(II) and coexisting metal ions and have important implications in Hg(II) chemical speciation and biogeochemical transformation, particularly in contaminated environments containing relatively high concentrations of Hg(II) and metal ions.

36 MATERIALS SCIENCE↗

PET-FBA: A lightweight enzyme allocation and thermodynamics-constrained flux analysis approach to explore Escherichia coli metabolic adaptation to intracellular acidification

Escherichia coli employs diverse strategies to adapt to acidic environments that disrupt enzyme activity and the thermodynamic feasibility of essential reactions. To understand the impact of pH stress on cell metabolism, we present the PET-FBA (pH-, Enzyme protein allocation-, and Thermodynamics-constrained Flux Balance Analysis) framework. PET-FBA extends genome-scale modeling by integrating enzyme protein costs and reaction Gibbs free energy changes. Additionally, by incorporating pH-dependent enzyme kinetics in response to intracellular acidification, this framework enables the simulation of E. coli's metabolic adjustments across varying external pH levels. The model's accuracy is validated by comparing in silico growth simulations with experimental measurements under both anaerobic and aerobic conditions, as well as in silico gene knockouts of essential genes. By explicitly incorporating pH effects, our model accurately replicates the metabolic shift towards lactate production as the primary fermentation product at low pH in anaerobic conditions. This shift is only predicted when enzyme kinetics are dynamically adjusted as a function of pH. Further analysis revealed that this shift can be attributed to the reduced protein efficiency of the acetyl-CoA branch compared to lactate dehydrogenase under acidic stress, which then becomes crucial for maintaining NAD regeneration and cell growth at low pH. Furthermore, we identified strategies for enhancing cell growth under acidic anaerobic conditions by improving the enzyme activity of lactate dehydrogenase and pyruvate formate lyase, which increases NAD production efficiency and reduces enzyme protein allocation costs. Designed as a lightweight yet versatile framework, PET-FBA enables efficient genome-scale metabolic analysis. Using E. coli as a model system, our framework provides a systematic approach to understanding metabolic responses to environmental stress, pinpointing key metabolic bottlenecks, and identifying potential targets for strain optimization.

42 ENGINEERING↗

Chemistry of Materials Underpinning Photoelectrochemical Solar Fuel Production

Since its inception, photoelectrochemistry has sought to power the generation of fuels, particularly hydrogen, using energy from sunlight. Efficient and durable photoelectrodes, however, remain elusive. Here we review the current state of the art, focusing our discussion on advances in photoelectrodes made in the past decade. We open by briefly discussing fundamental photoelectrochemical concepts and implications for photoelectrode function. We next review a broad range of semiconductor photoelectrodes broken down by material class (oxides, nitrides, chalcogenides, and mature photovoltaic semiconductors), identifying intrinsic properties and discussing their influence on performance. We then identify innovative in situ and operando techniques to directly probe the photoelectrode|electrolyte interface, enabling direct assessment of structure–property relationships for catalytic surfaces in active reaction environments. We close by considering more complex photoelectrochemical fuel-forming reactions (carbon dioxide and nitrogen reduction, as well as alternative oxidation reactions), where product selectivity imposes additional criteria on electrochemical driving force and photoelectrode architecture. By contextualizing recent literature within a fundamental framework, we seek to provide direction for continued progress toward achieving efficient and stable fuel-forming photoelectrodes.

08 HYDROGEN↗

Importance of the Heat Treatment Scheme on Self-Reducing Reactive Silver Inks

Self-reducing reactive silver inks can print high-quality silver at reasonable temperatures. While numerous studies have explored the impact of processing temperature on electrical properties, the role of the heat treatment scheme has not yet been studied. Common heat treatment schemes include printing and drying inks at room temperature before heat treatment, performing heat treatments while the inks are still wet, and directly printing the inks onto heated substrates. Each scheme generates distinct heat transfer and mass transport kinetics that can affect the silver morphology and electrical properties. However, to date, the impact of different schemes has not been systematically investigated. To address this knowledge gap, this work investigates how different heat treatment schemes impact metal formation, sintering, and the resultant electrical properties of printed self-reducing reactive silver inks. Heat treatment on room-temperature dried inks and wet inks, with top-down (oven) and bottom-up (hot plate) heating sources, were compared. Inks dried at room temperature resulted in extremely porous films that required high heat treatment temperatures (>100 °C) for silver densification. However, these dried films could only densify locally, and their high initial porosities resulted in voids and high resistances (~0.6 Ω mm –1 ) even after heat treatments above 300 °C. Inks that were wet during heat treatment showed moderate improvements in electrical properties with resistances on the order of 0.4 Ω mm –1 at heat treatments of 250 °C. Printing reactive inks directly onto heated substrates yielded the best low-temperature results, with 0.46 Ω mm –1 (5.5 × bulk silver) line resistances achieved at only 90 °C. Overall, this work’s experimental results provide detailed insights into why printing onto a heated substrate results in superior electrical performance compared to more common heat treatment schemes. Additionally, controlling where the precipitation reaction occurs is critical to controlling the film morphology and properties. As a result, this work shows that even an ammonia-based silver reactive ink can achieve good, low-temperature electrical properties with the proper heat treatment scheme.

14 SOLAR ENERGY↗

Conversion of CO 2 to Methanol and Ethanol on Pt/CeO x /TiO 2 (110): Enabling Role of Water in C–C Bond Formation

The surface chemistry of alcohol synthesis from CO 2 hydrogenation has been investigated using kinetic testing, ambient pressure x-ray photoelectron spectroscopy (AP-XPS) and DFT calculations over a multicomponent system where Pt and ceria nanoparticles coexisted on a titania template, Pt/CeO x /TiO 2 (110). Due to its high ability to bind and activate CO 2 , not seen for typical Cu-ZnO catalysts, the Pt-CeO x -TiO 2 interface is excellent for the hydrogenation of CO 2 to methanol with some ethanol also being produced (21% selectivity). The results of AP-XPS and DFT calculations indicate that the active state involves a mixture of Ti 4+ /Ti 3+ , Ce 3+ and Pt 0 /Pt + . A fast pathway for the formation of CH 3 O species is only plausible when Ce 3+ and Pt are present. The addition of water to the reaction feed facilitates the first hydrogenation of CO 2 and substantially enhances the surface coverage of C-containing species (CH 3 O, HCOO, CO 3 , CH x ), facilitating the formation of C-C bonds and the production of ethanol (38% selectivity).

36 MATERIALS SCIENCE↗

Operando High-Energy-Resolution X-ray Spectroscopy of Evolving Cu Nanoparticle Electrocatalysts for CO 2 Reduction

Advances in electrocatalysis research rely heavily on building a thorough mechanistic understanding of catalyst active sites under realistic operating conditions. Only recently have techniques emerged that enable sensitive spectroscopic data collection to distinguish catalytically relevant surface sites from the underlying bulk material under applied potential in the presence of an electrolyte layer. Here, we demonstrate that operando high-energy-resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) is a powerful spectroscopic method which offers critical surface chemistry insights in CO 2 electroreduction with sub-electronvolt energy resolution using hard X-rays. Combined with the high surface area-to-volume ratio of 5 nm copper nanoparticles, operando HERFD-XAS allows us to observe with clear evidence the breaking of chemical bonds between the ligands and the Cu surface as part of the ligand desorption process occurring under electrochemical potentials relevant for the CO 2 reduction reaction (CO 2 RR). In addition, the dynamic evolution of oxidation state and coordination number throughout the operation of the nanocatalyst was continuously tracked. With these results in hand, undercoordinated metallic copper nanograins are proposed to be the real active sites in the CO 2 RR. In conclusion, this work emphasizes the importance of HERFD-XAS compared to routine XAS in catalyst characterization and mechanism exploration, especially in the complicated electrochemical CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fe(porphyrin)-Catalyzed Alkene Epoxidation with NaOCl: A Practical Small- and Large-Scale Alternative to m CPBA

Epoxides are important intermediates in synthetic chemistry. Stoichiometric peroxyacids, such as meta -chloroperoxybenzoic acid ( m CPBA), are widely used to convert alkenes to epoxides but show poor compatibility with aromatic heterocycles and present hazards when scaled. Herein, we report a highly practical alkene epoxidation method that uses the commercially available iron porphyrin, Fe(TPFPP)Cl (TPFPP = tetrakis(pentafluorophenyl)porphyrin), as a catalyst (0.05 mol %) and aqueous NaOCl as the oxidant in acetonitrile as the solvent. No additional ligands or additives are needed, and the reactions proceed under ambient conditions. The method shows a broad scope, affording high yields of epoxides in reactions with terminal and internal aromatic and aliphatic alkenes, heterocycle-containing substrates, glycals, and polyenes. The practicality of the method is demonstrated in the 100 g scale epoxidation of tri- O -acetyl- D -glucal, which proceeds to completion in 15 min at room temperature.

catalysts↗

Pyrocumulonimbus Events Over British Columbia in 2017: An Ensemble Model Study of Parameter Sensitivities and Climate Impacts of Wildfire Smoke in the Stratosphere

Abstract The Pyrocumulonimbus (pyroCb) events over British Columbia in 2017 were observed in the lower stratosphere for about 8–10 months after the smoke injections. Several previous studies used global climate models to investigate the physical parameters for the 2017 pyroCb events, but the conclusions show strong model dependency. In this study, we use the Energy Exascale Earth System Model (E3SM) and complete an ensemble of runs exploring three injection parameters: smoke aerosol mass, the percentage of black carbon within the smoke aerosols, and plume injection height. Additionally, we consider the heterogeneous reaction of ozone and primary organic matter. According to the satellite daily observed aerosol optical depth (AOD), we find that the best ensemble member is the simulation with 0.4 Tg of smoke, 3% of which is black carbon, a 13.5 km smoke injection height, and a 10 −5 probability factor of the heterogeneous reaction. Besides AOD, we examine the ensemble score based on the metrics used in previous studies: the metrics of the extinction coefficient at 18 km altitude and the maximum plume height. The conclusion of the best estimate of the injection parameters for 2017 pyroCb events shows strong not only model but also evaluation metric dependency. We use the Random Forest machine learning technique to quantify the relative importance of each parameter in accurately simulating the 2017 pyroCb events and find that the injection height is the most critical feature, no matter which metric is used to score the ensemble members.

54 ENVIRONMENTAL SCIENCES↗

Experimental studies on photoabsorption by endohedral fullerene ions with a focus on Xe@C 60 + confinement resonances

A brief overview on the status of experimental investigations into photoionization and fragmentation of fullerenes and endohedral fullerenes by absorption of a single short-wavelength photon is presented. The focus of this paper is on the endohedral Xe@C 60 + molecular ion in which a xenon atom is centrally encapsulated inside a C$^{+}_{60}$ fullerene cage. Confinement resonances that result from the interference of Xe photoelectron matter waves emerging from the C$^{+}_{60}$ cavity were studied by exposing Xe@C 60 + ions to synchrotron radiation of 60 to 150 eV energy which is the region of the well-known giant atomic Xe 4d excitation resonance. Photoions Xe@C n q+ (with final charge states q = 2,3,4 of the product ions and numbers of carbon atoms left in the cage) were recorded as a function of photon energy and cross sections for the individual reaction channels were determined. In addition to previous work, new final channels (q = 2; n = 60, 58 and q = 4; n = 58, 56) were observed, and thus, about 70% of the oscillator strength expected for the encapsulated Xe atom in the investigated energy range could be recovered. The present results establish the first and, so far, only conclusive experimental observation of confinement resonances in an endohedral fullerene. The data are in remarkable agreement with relativistic R-matrix calculations that accompanied the previous experimental work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A high-temperature sample changer for parallelized in situ X-ray studies to efficiently explore reaction space

A sample environment for high-throughput X-ray scattering studies in transmission geometry to probe the mechanism and kinetics of moderate-temperature reactions in solution, molten fluxes and solids is described. This high-temperature sample changer enables efficient studies of reactions that are slow relative to the timescale of the X-ray scattering measurements by allowing up to 18 samples to be probed at the same temperature in parallel. This significantly enhances the throughput ofin situX-ray scattering studies as the sample changer effectively facilitates systematic studies that compare different reaction parameters (e.g.concentration, precursor, composition, additives), reference samples (e.g.background, pure precursors) and replicates (to demonstrate reproducibility) with enhanced consistency afforded by the quasi-simultaneous nature of the measurements. The large sample volumes, compared with those typically used for X-ray scattering measurements, are on a similar scale to those in the laboratory, making the results more directly comparable.

Chemistry↗

DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys

A density functional theory investigation of the process of dissolution of Ni and Cr adatoms from model Ni–Cr(111) alloy surfaces is presented, both in vacuum and with explicit water molecules. The goal is to understand how the electronic structures solved using DFT can provide insights as to changes in valence, energy and coordination of the adatoms in the process of dissolving from the alloy surface. It is found that nearby Cr solute atoms increase the dissolution activation energy of Ni. Cr adatoms have a similar dissolution activation energy as Ni adatoms, except for one particular surface configuration that has a much smaller dissolution activation energy, which might promote selective dissolution of Cr in Ni–Cr alloys. To interpret the first-principles modeling results for the potential energy trajectory along the dissolution reaction coordinate, we provide a thermodynamic breakdown of the various terms that contribute to the dissolution activation and total reaction energy. The role of addition of Cr is explored on the dissolution kinetics of a Ni–Cr alloys of varying composition by constructing a model for the corrosion current density with DFT-based activation energies. Lastly, dissolution resistance index is proposed as a quantifiable descriptor of the dissolution resistance of corrosion resistant alloys.

36 MATERIALS SCIENCE↗

In situ neutron and synchrotron diffraction of La0.9Sr0.1Co1-yFeyO3 (y=0, 0.25, 0.75, 1)

Powder La0.9Sr0.1Co1-yFeyO3 (y=0, 0.25, 0.75, 1) samples were probed via in situ neutron (POWGEN, Spallation Neutron Source, Oak Ridge National Laboratory) and synchrotron (11-BM, Advanced Photon Source, Argonne National Lab) diffraction cycling between methane and air at temperatures ranging from room temperature to 850 C. Mail in neutron data (POWGEN) was collected on the samples at room temperature and 10 K. Additionally, gas production under similar reaction conditions as the in situ diffraction as monitored by Gasboard 3100 (California State University, Fullerton) is also included.

catalysis↗

Accurate determination of production data of the non-standard positron emitter 86 Y via the 86 Sr(p,n)-reaction

In view of several significant discrepancies in the excitation function of the 86 Sr(p,n) 86g+xm Y reaction which is the method of choice for the production of the non-standard positron emitter 86 Y for theranostic application, we carried out a careful measurement of the cross sections of this reaction from its threshold up to 16.2 MeV at Forschungszentrum Jülich (FZJ) and from 14.3 to 24.5 MeV at LBNL. Thin samples of 96.4% enriched 86 SrCO 3 were prepared by sedimentation and, after irradiation with protons in a stacked-form, the induced radioactivity was measured by high-resolution γ -ray spectrometry. The projectile flux was determined by using the monitor reactions nat Cu(p,xn) 62,63,65 Zn and nat Ti(p,x) 48 V, and the calculated proton energy for each sample was verified by considering the ratios of two reaction products of different thresholds. Additionally, the experimental cross section data obtained agreed well with the results of a nuclear model calculation based on the code TALYS. From the cross section data, the integral yield of 86 Y was calculated. Over the optimum production energy range E p = 14 → 7 MeV the yield of 86 Y amounts to 291 MBq/μA for 1 h irradiation time. This value is appreciably lower than the previous literature values calculated from measured and evaluated excitation functions. It is, however, more compatible with the experimental yields of 86 Y obtained in clinical scale production runs. The levels of the isotopic impurities 87m Y, 87g Y, and 88 Y were also estimated and found to be <2% in sum.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

C-C Coupling Mechanism on Cu(100) A Molecular Dynamics Study at 298K

The electrochemical reduction of carbon dioxide (CO2) into valuable fuels such as C1 (syngas, methane) and C2 (ethylene, ethanol) products is a key strategy for achieving a carbon-neutral economy. Computational studies of C-C coupling, a critical step in CO2 reduction, are essential for designing more efficient catalysts. However, simulating these processes under realistic electrochemical conditions, including temperature and solvent effects, is computationally demanding. In this work, we develop a machine learning-based atomistic potential to study CO2 reduction on Cu(100) surfaces, accounting for temperature and explicit water solvent effects. We compute thermodynamic free energies of the possible C-C coupling pathways, CO*+CO*→OCCO*, CO*+CHO*→OCCHO*, CO*+COH*→OCCOH*, CHO*+COH*→OHCCOH*, COH*-COH*→HOCCOH*, and CHO*-CHO*→OHCCHO*. Our results quantify the thermodynamic tendencies of these reactions and reveal that, in addition to the well-established CO* + CO* → OCCO* pathway, CHO* is a critical intermediate in the formation of C2 products on Cu(100). Furthermore, we demonstrate that the machine learning approach offers a cost-efficient framework for studying CO2 reduction on diverse catalysts under realistic electrochemical conditions.

machine learning↗