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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

Exercising direct control over the unusual electronic structures arising from quantum confinement effects in graphene nanoribbons (GNRs) is intimately linked to geometric boundary conditions imposed by the structure of the ribbon. Besides composition and position of substitutional dopant atoms, the symmetry of the unit cell, width, length, and termination of a GNR govern its electronic structure. Here, we present a rational design that integrates each of these interdependent variables within a modular bottom-up synthesis. Our hybrid chemical approach relies on a catalyst-transfer polymerization that establishes excellent control over length, width, and end groups. Complemented by a surface-assisted cyclodehydrogenation step, uniquely enabled by matrix-assisted direct (MAD) transfer protocols, geometry and functional handles encoded in a polymer template are faithfully mapped onto the structure of the corresponding GNR. Bond-resolved scanning tunneling microscopy (BRSTM) and spectroscopy (STS) validate the robust correlation between polymer template design and GNR electronic structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Generation, Transfer, and Loss of Alternative Oxidase Paralogues in the Aspergillaceae Family

Alternative oxidase (Aox) is a terminal oxidase operating in branched electron transport. The activity correlates positively with overflow metabolisms in certain Aspergilli, converting intracellular glucose by the shortest possible path into organic acids, like citrate or itaconate. Aox is nearly ubiquitous in fungi, but aox gene multiplicity is rare. Nevertheless, within the family of the Aspergillaceae and among its various species of industrial relevance—Aspergillus niger, A. oryzae, A. terreus, Penicillium rubens—paralogous aox genes coexist. Paralogous genes generally arise from duplication and are inherited vertically. Here, we provide evidence of four independent duplication events along the lineage that resulted in aox paralogues (aoxB) in contemporary Aspergillus and Penicillium taxa. In some species, three aox genes are co-expressed. The origin of the A. niger paralogue is different than that of the A. terreus paralogue, but all paralogous clades ultimately arise from ubiquitous aoxA parent genes. We found different patterns of uncorrelated gene losses reflected in the Aspergillus pedigree, albeit the original aoxA orthologues persist everywhere and are never replaced. The loss of acquired paralogues co-determines the contemporary aox gene content of individual species. In Aspergillus calidoustus, the two more ancient paralogues have, in effect, been replaced by two aoxB genes of distinct origins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Performance of the Particle-Identification Silicon-Telescope Array coupled with the VAMOS++ magnetic spectrometer

The Particle-Identification Silicon-Telescope Array (PISTA) is a new detection system designed for high-resolution studies of fission process induced by multi-nucleon transfer in inverse kinematics. It is specifically optimized for experiments with the VAMOS++ magnetic spectrometer at GANIL (Grand Accélérateur National d’Ions Lourds). The array comprises eight trapezoidal ΔE-E silicon telescopes arranged in a lamp shade configuration. Each telescope integrates two single-sided stripped silicon detectors, enabling target-like recoil identification, energy loss measurements, and trajectory reconstruction. Positioned in close proximity to the target, PISTA’s compact geometry achieves high-efficiency tracking of target-like recoils produced in multi-nucleon transfer reactions at Coulomb barrier energies. The spatial segmentation of the array allows precise determination of the mass and charge of the target-like nucleus, and excitation energy of fissioning systems. This work presents the particle identification and excitation energy reconstruction performances for the interactions of 238 U beam with 12 C target. An excitation energy resolution of 800 keV (FWHM) was determined together with mass resolution of 1.1% (FWHM). The combination of PISTA and VAMOS++ magnetic spectrometer enables unprecedented investigations of the fission process as a function of the excitation energy of the fissioning nucleus, particularly for exotic systems produced in transfer-induced reactions.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Efficient Mesofluidic Separation of Large Particles in nuclear slurries - 20408

Efficient and effective particle separation is essential to cleanup of many nuclear wastes. For example, particle separation may be used to accelerate settle-decant bottlenecks that limit the throughput necessary to achieve the U.S. Department of Energy waste cleanup mission in a timely manner. Particle separation may be used to protect downstream processing equipment from pulses of solids that may be encountered near (within a few feet of) liquid-solid interfaces during waste transfer operations, thereby preventing work stoppages. Effective particle separation may permit efficient sludge washing. These are only a few of the ways in which particle separation is important. Yet, efficient and effective particle separation in nuclear processing environments remains challenging. For example, settle-decant operations permit larger and heavier particles to settle, leaving smaller, lighter particles suspended. However, settle-decant operations are slow, convection currents may resuspend solids, hindered settling of multicomponent slurries remains incompletely understood, and predictive models for settling in graduated cylinders fail to match limited observations of settling in large waste tanks. Additionally, pumping operations can cause turbulent resuspension of particles when the pump intake is close to the settled solids layer. Filtration techniques that use membranes or partially permeable barriers retain larger particles, permitting smaller particles to permeate. However, filters, including dead-end filtration, are prone to clogging and caking, operate at elevated pressures due to minimal void volume, and increase in pressure during operations, which require more control systems. Therefore, the need for high throughput particle separation techniques that operate with modest pressure drops persists. A novel mesofluidic separator presents the opportunity to effectively and efficiently accelerate the waste cleanup mission. The separator separates large particles from process streams across a broad range of particle sizes and has no moving parts or media to replace, regenerate, or clean. This separator design has an unusually large void volume, permitting operation at much higher flow rates (and lower pressures) than traditional filtration (e.g., dead-end filtration). Industrial-scale flow rates have been demonstrated. In performance testing, mesofluidic separators operate at might flow rates (>90 gpm (0.0006 m{sup 3}/s) in piping 3 inches (0.08 m) in diameter; Re>10{sup 5}), with modest pressure drop (∼25 psi (170 KPa) in testing). In complex, aggregating waste simulants, the separator loses <25% of flow projected over months without back pulsing or chemical cleaning. Mesofluidic separation presents infrastructure advantages, reduces risk, and provides mission impact. Infrastructure advantages include implementation within existing transfer systems, plug and play without facility modifications to safety systems, and operation at low pressures. The separator is flexible in location, may be positioned within or outside of waste tanks, and may replace or augment dead-end and cross-flow filters. Mesofluidic separation reduces risk by minimizing waste (no media to replace or regenerate and no cleaning chemicals to handle and dispose) and by minimizing filter change-out consistent with as low as reasonably achievable (ALARA) exposure to workers. The potential mission impact of these separators is substantial. The separator has potential to support, simplify, and accelerate in-farm transfers and waste feed delivery. Furthermore, the separator can free up settling and holding tanks in the Direct Feed Low-Activity Waste (DFLAW) mission by reducing or eliminating post-transfer settling and wait times with the potential to free up 1 Mgal (4000 m{sup 3}) of double-shell tank space. This paper quantitatively compares mesofluidic separation to dead-end filtration, discusses scale-up results, and considers the separator's potential to efficiently and effectively reduce the long-term environmental ability of particulate-rich nuclear wastes. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Role of Intact Hydrogen-Bond Networks in Multiproton-Coupled Electron Transfer

The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole–phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-protoncoupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (~1000 mV s –1 ) a chemically reversible process is observed with an E 1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s –1 ) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. Furthermore, this work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.

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

Aromatic heterobicycle-fused porphyrins: impact on aromaticity and excited state electron transfer leading to long-lived charge separation

A new synthetic method to fuse benzo[4,5]imidazo[2,1-a]isoindole to the porphyrin periphery at the β,β-positions has been developed, and its impact on the aromaticity and electronic structures is investigated. Reactivity investigation of the fused benzoimidazo-isoindole component reveals fluorescence quenching of a zinc porphyrin (AMIm-2) upon treatment with a Brønsted acid. The reaction of the zinc porphyrin (AMIm-2) with methyl iodide initiated a new organic transformation, resulting in the ring-opening of isoindole with the formation of an aldehyde and dimethylation of the benzoimidazo component. The fused benzoimidazo-isoindole component acted as a good ligand to bind platinum(II), forming novel homobimetallic and heterobimetallic porphyrin complexes. The fusion of benzoimidazo-isoindole on the porphyrin ring resulted in bathochromically shifted absorptions and emissions, reflecting the extended conjugation of the porphyrin π-system. Time-resolved emission and transient absorption spectroscopy revealed stable excited state species of the benzoimidazo-isoindole fused porphyrins. Zinc porphyrin AMIm-2 promoted excited state electron transfer upon coordinating with an electron acceptor, C60, generating a long-lived charge-separated state, in the order of 37.4 μs. The formation of the exceptionally long-lived charge-separated state is attributed to the involvement of both singlet and triplet excited states of AMIm-2, which is rarely reported in porphyrins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrogenerated Chemiluminescence of Near-Infrared-Emitting CdSe@CdSe Nanorods in Aqueous Solution

Electrogenerated chemiluminescence (ECL) was observed from TOPO-capped CdSe@CdSe nanorods (NRs) depositing on a metal electrode in phosphate buffer solution (PBS). Two ECL peaks at -1.05 and -1.33 V in pH 9.2, 0.1 M PBS were found under cyclic voltammetric conditions. Cyclic voltammetry of this solution displayed no distinctive features, on the other hand, light emission was observed during cyclic potential scans. Additionally, the photoluminescence (PL) spectrum showed an emission maximum at 692 nm. The spectrum of ECL possesses one peak which coincides very well with the PL spectrum of the nanorods film. The mechanism for ECL peaks was proposed. Electron transfer reactions between charged nanorods and molecular redox-active coreactants such as dissolved oxygen and H2O2 or between positively and negatively charged nanorods occurred that led to electron and hole annihilation, producing light.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Data-Centric AI and the Open Energy Data Initiative (OEDI)

This presentation emphasizes the critical importance of data-centric AI. The limitations of model-centric AI when dealing with poor or insufficient data are highlighted, and it is illustrated how training models on inaccurate or noisy data leads to suboptimal results. This talk advocates for a hybrid approach that combines a focus on data quality and model parameters to achieve optimal results. The Open Energy Data Initiative (OEDI) is introduced as a valuable resource for obtaining high-quality energy-related datasets, hosting nearly 2,000 publicly accessible datasets, including 99 solar-related datasets, totaling over 2.7 petabytes of data. OEDI's data lakes enable users to query and work with data without extensive transfers. In conclusion, the significance of data-centric AI and adherence to data curation best practices is emphasized, positioning OEDI as a prime source of high-quality data for AI and machine learning in the renewable energy sector.

AI↗
DOE OSTI2021

Propagation of positive discharges in an air bubble having an embedded water droplet

Low temperature plasmas generated inside gas bubbles immersed in water is an effective method of rapidly transferring plasma generated reactive species to the water for applications in biomedicine, agriculture and environment. Reactive species are generally produced in the gas phase plasma and then solvate into the liquid. The large surface-to-volume ratio (SVR) of the bubble accelerates this process. In generating bubbles in water, aerosols and droplets are also contained within the bubble. These droplets also have a large SVR and so can be rapidly plasma activated. However, the presence of the droplets can also impact the propagation of the plasma in the bubble. In this paper, results are discussed from computational and experimental investigations of the formation and evolution of discharges in an air bubble immersed in water with an embedded water droplet. The computations were performed with a two-dimensional plasma hydrodynamics model. Experiments were performed with a quasi-2D bubble apparatus. In bubbles having a droplet, a plasma filament typically bridges from the powered electrode to the droplet, and then from the droplet to the bubble surface. A surface-hugging streamer also occurs on the inner bubble surface and on the surface of the droplet. Both surface streamers result in part from surface charge accumulation and can dominate the formation of reactive species that transport into the droplet. Increasing droplet conductivity suppresses propagation of the surface discharge and leads to a lower density of aqueous reactive species. Increasing conductivity of the surrounding water does not change the overall structure of the discharge but does slightly elevate the discharge intensity. Finally, the size and shape of the embedded droplet can significantly affect the formation and propagation of the streamer.

2D fluid modelling↗
DOE OSTI2024

Field Validation of MVA Technology for Offshore CCS: Novel Ultra-High-Resolution 3D Marine Seismic Technology (P-Cable) (Final Report)

The objectives of the proposed study were to deploy and validate a specific monitoring technology, high-resolution 3D marine seismic (HR3D), appropriate for large-demonstration and commercial-scale offshore CCS sites. The project accomplished successful acquisition two HR3D seismic surveys. The first HR3D dataset was over the offshore injection site of the Tomakomai, Japan integrated pilot CCS project, which at the time of survey acquisition was actively injecting CO 2 . The first survey also represented a successful international collaboration between the DOE NETL program and Japan’s national CCS program and was the first successful acquisition and use of HR3D over an active CO 2 injection site (Meckel, Feng et al. 2019). The Tomakomai HR3D survey successfully tested a novel 4-streamer HR3D system array in which, for the first time, no cross-cable (aka “P-Cable”) was utilized and only four GeoEel streamers were used instead of the standard 12-streamer configuration. Consequently, this was not, strictly speaking, a deployment of the “P-Cable” system of (Planke and Berndt 2004) but rather a modified version, thereof, and it is the first known demonstration of the modified system configuration. One very positive outcome from the Japanese collaboration earlier in the project was the ability to learn from the Japanese how they used tail buoys with GPS to determine the position of the seismic source and receivers in time and space. Based on that experience, GCCC designed and built six GPS receivers that could be used to position the streamer receivers and the seismic source via tail buoys. A fundamental advance that was made on the original design, was the ability to directly power the tail buoy GPS units and transfer data through the streamers (i.e., vs. the batteries used at Tomakomai). The bulkiness of the GPS batteries caused drag and episodic surging of the buoys, which affected data quality by lifting up the tail end of the streamers so the receivers were not at the same depth. The units were tested onshore for accuracy and functionality, and the design was subsequently and successfully tested in marine acquisition mode during the SLP survey acquisition. The marine acquisition test and survey satisfied Subtasks 2.2.2, Novel Positioning Technology Selection and Subtask 2.2.3, Novel Positioning Technology Deployment. Results of the novel positioning technology selection (Subtask 2.2.2) were considered successful and will be incorporated in future HR3D seismic acquisition projects to reduce costs, improve deployment safety at sea, and integrate both seismic and data recording via a single data transfer through the streamers to the recording system. The project also established a permitting process through NETL NEPA compliance, which included an Environmental Assessment in a marine setting and is required for conducting these types of surveys using Federal funding. The permitting process charted a “boilerplate,” which can allow future surveys related to other funded projects to move forward more expeditiously. Future improvements that could be considered are more robust seals on the GPS module and stronger materials (especially joints) on tail buoy fabrication. These would increase fixed costs, but would be advisable and probably more economic long-term if multiple HR3D surveys are planned. Project Accomplishments include: • Pre-survey Sensitivity Study • Marine geochemistry methods and data analysis • Successful HR3D seismic dataset acquired @ Tomakomai active CO 2 injection marine site • Developed advanced seismic processing techniques • No NRMS anomalies detected in overburden; Demonstration of containment • Repeatability study • Second survey collected @ San Luis Pass, TX • 4D application using positioning techniques developed in the project for monitoring were successful

3D seismic GPS positioning↗
DOE OSTI2024

Structural Asymmetry and Chiral-Induced Spin Selectivity in Chiral Palladium-Halide Semiconductors

Chiral Pb-free metal-halide semiconductors (MHSs) have attracted considerable attention in the field of spintronics due to various interesting spin-related properties and chiral-induced spin selectivity (CISS) effect. Despite their excellent chemical and structural tunability, the material scope and crystal structure of Pb-free chiral MHSs exhibiting the CISS effect are still limited; chiral MHSs that have metal-halide structures of octahedra and tetrahedra are only reported. Here, we report a new class of chiral MHSs, of which palladium (Pd)-halides are formed in 1D square-pyramidal structures or 0D square-planar structures, with a general formula of ((R/S-MBA) 2 PdBr 4 ) 1-x ((R/S-MBA) 2 PdCl 4 ) x (MBA = methylbenzylammonium; x = 0, 0.25, 0.5, 0.75, and 1) for the first time. The crystals adopt the 1D helical chain of Pd-halide square-pyramid (for x = 0, 0.25, 0.5, and 0.75) and 0D structure of Pd-halide square-plane (for x = 1). All the Pd-halides are distorted by the interaction between the halide and the chiral organic ammonium and arranged in a noncentrosymmetric position. Circular dichroism (CD) for ((R/S-MBA) 2 PdBr 4 ) 1-x ((R/S-MBA) 2 PdCl 4 ) x indicates that chirality was transferred from chiral organic ammonium to Pd-halide inorganics. ((R-MBA) 2 PdBr 4 ) 1-x ((R-MBA) 2 PdCl 4 ) x (x = 0, 0.25, 0.5, and 0.75) shows a distortion index of 0.127-0.128, which is the highest value among the previously reported chiral MHSs to the best of our knowledge. We also find that (R/S-MBA) 2 Pd(Br 1-x Cl x ) 4 crystals grow along the out-of-plane direction during spin coating and have high c-axis orientation and crystallinity, and (R/S-MBA) 2 Pd(Br 1-x Cl x ) 4 (x = 0 and 0.5) crystals exhibit a CISS effect in polycrystalline bulk films. In conclusion, these results demonstrate the possibility of a new metal-halide series with square-planar structures or square-pyramidal structures for future spintronic applications.

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

Transient methods for understanding the properties of strongly oxidizing radicals

This review discusses the properties of strongly oxidizing radicals in organic and aqueous media and highlights the challenges in obtaining accurate values of their reduction potentials. Transient redox equilibrium methods based on the use of strong photooxidants or initiated by pulse radiolysis are shown to provide versatile approaches for decoupling electron transfer reactions from follow-up reactivity of unstable radical species, resulting in accurate values of reduction potentials of very positive couples, including some solvent radical cations. Here, we also show that correlations of reduction potentials with Hammett Σσ + p parameters, as well as gas phase ionization potentials, can be used to estimate the redox properties of unknown couples within a homologous series of compounds. The effects of ion pairing and hemicolligation on redox properties of organic and inorganic radicals are also discussed.

14 SOLAR ENERGY↗
DOE OSTI2025

Hydrogen density mapping in biomolecular crystals through dynamic nuclear polarization

Many fundamental biological processes, including those in photosynthetic reaction centers and enzyme active sites, involve charge and energy transfer, bond cleavage, protonation and hydrogen bonding. Because H atoms play such central roles in these reactions, accurately determining their positions is essential. Yet, conventional X-ray crystallography primarily resolves the heavy atoms in biological structures and provides limited insight into hydrogen, even at atomic resolution. Neutron macromolecular crystallography (NMC) overcomes this limitation by offering exceptional sensitivity to hydrogen and deuterium. Here, we present a theoretical framework for the development of dynamic nuclear polarization NMC (DNP-NMC) techniques, which exploit the alignment of neutron and proton nuclear spins to enhance and tune the hydrogen signal contribution. The DNP-NMC approach advances the resolution of H atoms within biomolecular crystals, whether bound to protein residues or present in solvent. The method establishes key relationships for the coherent structure factor of polarized neutron scattering from hydrogenous matter. It theoretically achieves full accuracy in phase reconstruction and offers a path to improve neutron structure determination, achieving accuracies exceeding ≳80% by incorporating titration states. Using a variant of the hybrid input/output phase-retrieval algorithm, it allows recovery of the hydrogen density with ≳90% phase accuracy. In conclusion, we further discuss sources of experimental uncertainty for the upcoming DNP-enabled, quasi-Laue IMAGINE-X experiment at Oak Ridge National Laboratory's High Flux Isotope Reactor.

dynamic nuclear polarization↗
DOE OSTI2021

Cost-Performance Trade-off in thermoelectric air conditioning system with graded and constant material properties

Thermoelectric (TE) air cooling is a solid-state technology that has the potential to replace conventional vapor compression-based air conditioning. In this paper, we present a detailed system-level modeling for thermoelectric air conditioning system with position-dependent (graded) and constant material properties. Strategies for design optimization of the system are provided in terms of cost-performance trade-off. Realistic convection heat transfer at both sides of the system are taken into account in our modeling. Here, the effects of convection heat transfer coefficients, air flowrate, and thermoelectric material properties are investigated with varying key parameters such as TE leg thickness, module fill factor, and input current. Both constant material properties and graded properties are considered for the TE materials, and they are compared in terms of the degree of cooling, coefficient of performance (COP), and power consumption. For graded materials, we employ one-dimensional finite element methods to solve the coupled electrical and thermal current equations with arbitrary profile of material properties varying with position along the TE legs. We find that graded materials can enhance the degree of cooling, but only at the expense of COP, compared to the case of constant property materials. With constant material properties of ZT = 1 and relatively low electric current, the power consumption of TE coolers can be lower than those of conventional air conditioners at an equivalent cooling capacity. Considering additional advantages such as demand-flexible operation, low noise, and high scalability, thermoelectric cooling could be a competitive technology for future air conditioning applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Mutation of active site glutamate in serine hydroxymethyltransferase allows trapping a reactive intermediate: a combined neutron and X-ray crystallography study

Serine hydroxymethyltransferase (SHMT) is a pyridoxal-5′-phosphate (PLP) dependent enzyme that catalyzes a chemical transformation essential for the one-carbon (1C) metabolism. SHMT reversibly converts L-Ser into Gly and transfers a 1C unit to tetrahydrofolate (THF) to give 5,10-methylene-THF (5,10-MTHF). 5,10-MTHF, a 1C-unit donor, plays a crucial role in the downstream biomolecular syntheses required for the cell homeostasis and proliferation. SHMT is a prominent target for the drug discovery to battle bacterial and parasitic infections, and to treat various types of cancer. SHMT-catalyzed chemistry is governed by the general acid-base catalysis. Knowledge of the catalytic mechanism can aid drug design but can only be achieved when the atomic details of each reaction step are mapped, including accurate determination of hydrogen atom positions. Here we utilized the inactive E53Q mutant of Thermus thermophilus ( Tth ) SHMT to directly determine protonation states with room-temperature neutron crystallography and to capture a reactive intermediate containing the PLP-L-Ser external aldimine and THF in the enzyme active site. We observed protonation of the Schiff base nitrogen (N SB ) in the PLP internal aldimine but no change in the protonation states of other ionizable PLP groups and active site residues compared to wild-type Tth SHMT. X-ray structural analysis of the ternary intermediate complex E53Q-Ser-THF that eluded previous structural characterization shows the strategic positioning of the E53Q side chain in close proximity to the external aldimine and THF and reinforces the proposed role for E53 as the driver of proton transfer events along the reaction pathway.

Drago, Victoria N. [Oak Ridge National Laboratory ↗
DOE OSTI2023

Elucidating the Molecular Origins of the Transference Number in Battery Electrolytes Using Computer Simulations

The rate at which rechargeable batteries can be charged and discharged is governed by the selective transport of the working ions through the electrolyte. Conductivity, the parameter commonly used to characterize ion transport in electrolytes, reflects the mobility of both cations and anions. The transference number, a parameter introduced over a century ago, sheds light on the relative rates of cation and anion transport. This parameter is, not surprisingly, affected by cation–cation, anion–anion, and cation–anion correlations. In addition, it is affected by correlations between the ions and neutral solvent molecules. Computer simulations have the potential to provide insights into the nature of these correlations. We review the dominant theoretical approaches used to predict the transference number from simulations by using a model univalent lithium electrolyte. In electrolytes of low concentration, one can obtain a quantitative model by assuming that the solution is made up of discrete ion-containing clusters–neutral ion pairs, negatively and positively charged triplets, neutral quadruplets, and so on. These clusters can be identified in simulations using simple algorithms, provided their lifetimes are sufficiently long. In concentrated electrolytes, more clusters are short-lived and more rigorous approaches that account for all correlations are necessary to quantify transference. Elucidating the molecular origin of the transference number in this limit remains an unmet challenge.

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

Directed self-assembly of block copolymers for high-precision patterning in the era of extreme ultraviolet lithography

Extreme ultraviolet (EUV) lithography enables unprecedented resolution in semiconductor patterning but faces critical challenges in developing resist materials that achieve high-precision at economically viable throughput. Directed self-assembly (DSA) of block copolymers (BCPs) offers a promising solution for pattern rectification by leveraging thermodynamically determined domain structures to decouple BCP pattern quality from the imperfect original lithographic pattern. This prospective presents an overview of recent progress on the EUV + DSA strategy, covering advances in BCP material design, processing, metrology, and pattern transfer. We highlight recent advances in high-χ BCPs with perpendicular orientation and domain spacings compatible with EUV dimensions, leveraging A-b-(B-r-C) architectures. We also discuss progress in chemical pre-pattern fabrication using both positive- and negative tone resists, along with processing strategies to minimize defects and roughness based on BCP thermodynamics and assembly kinetics. We further examine metrology platforms for characterizing the thermodynamics of BCP materials and quantifying the size and shape of BCP domains. Lastly, we review pattern transfer strategies for generating functional inorganic masks suitable for semiconductor manufacturing. Together, these advances highlight the potential of DSA to complement EUV lithography, offering a pathway to address critical challenges in achieving high-precision patterning for the semiconductor industry.

Lee, Kyunghyeon [Univ. of Chicago, IL (United Stat↗
DOE OSTI2021

Role of redox-active biochar with distinctive electrochemical properties to promote methane production in anaerobic digestion of waste activated sludge

Biochar has been reported as an effective additive to improve methane production during anaerobic digestion (AD). However, the mechanism for such a stimulatory impact remains unclear. Here we investigated the capability of three pyrolytic biochars with distinctive electrochemical properties (BC300, BC500, BC700) to promote methanogenic performance of anaerobic digesters treating waste activated sludge (WAS). The cumulative methane production and the maximum methane production rate were increased by 46.9% and 181.6%, respectively, with BC300 amendment. By characterizing the electrochemical properties of biochar, our research team found out that methane production in AD of sludge was positively correlated to biochar’s electron-donating capacity (EDC) rather than its bulk electrical conductivity. These results indicate that the electron transfer mediated by the redox-active functional groups may prevail over the direct electron migration as the predominant mechanism to facilitate interspecies electron transfer in syntrophic communities for enhanced methanogenesis. Microbial community analysis suggests that biochar enriched Methanosarcina and Methanobacterium. Overall, this study shows that functional groups-mediated electron transfer contributes greatly to the improved methane production in WAS digester with biochar amendment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗