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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 1,045 records · Page 58
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Fast Charge‐Transfer Rates in Li‐CO 2 Batteries with a Coupled Cation‐Electron Transfer Process

Li-CO 2 batteries with a high theoretical energy density (1876 Wh kg −1 ) have unique benefits for reversible carbon fixation for energy storage systems. However, due to lack of stable and highly active catalysts, the long-term operation of Li-CO 2 batteries is limited to low current densities (mainly <0.2 mA cm −2 ) that are far from practical conditions. In this work, it is discovered that, with an ionic liquid-based electrolyte, highly active and stable transition metal trichalcogenide alloy catalysts of Sb 0.67 Bi 1.33 X 3 (X = S, Te) enable operation of the Li-CO 2 battery at a very high current rate of 1 mA cm −2 for up to 220 cycles. It is revealed that: i) the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, ii) a coupled cation-electron charge transfer process facilitates the carbon dioxide reduction reaction (CO 2 RR) occurring during discharge, and iii) the concentration of ionic liquid in the electrolyte controls the number of participating CO 2 molecules in reactions. A combination of these key factors is found to be crucial for a successful operation of the Li-CO 2 chemistry at high current rates. This work introduces a new class of catalysts with potential to fundamentally solve challenges of this type of batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Improving Data and Prediction Quality of High-Throughput Perovskite Synthesis with Model Fusion

Combinatorial fusion analysis (CFA) is an approach for combining multiple scoring systems using the rank-score characteristic function and cognitive diversity measure. One example is to combine diverse machine learning models to achieve better prediction quality. In this work, we apply CFA to the synthesis of metal halide perovskites containing organic ammonium cations via inverse temperature crystallization. Using a data set generated by high-throughput experimentation, four individual models (support vector machines, random forests, weighted logistic classifier, and gradient boosted trees) were developed. We characterize each of these scoring systems and explore 66 possible combinations of the models. When measured by the precision on predicting crystal formation, the majority of the combination models improves the individual model results. The best combination models outperform the best individual models by 3.9 percentage points in precision. In addition to improving prediction quality, we demonstrate how the fusion models can be used to identify mislabeled input data and address issues of data quality. In particular, we identify example cases where all single models and all fusion models do not give the correct prediction. Experimental replication of these syntheses reveals that these compositions are sensitive to modest temperature variations across the different locations of the heating element that can hinder or enhance the crystallization process. In summary, we demonstrate that model fusion using CFA can not only identify a previously unconsidered influence on reaction outcome but also be used as a form of quality control for high-throughput experimentation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Timescale Separation of Positive and Negative Signaling Creates History-Dependent Responses to IgE Receptor Stimulation

The high-affinity receptor for IgE expressed on the surface of mast cells and basophils interacts with antigens, via bound IgE antibody, and triggers secretion of inflammatory mediators that contribute to allergic reactions. To understand how past inputs (memory) influence future inflammatory responses in mast cells, a microfluidic device was used to precisely control exposure of cells to alternating stimulatory and non-stimulatory inputs. We determined that the response to subsequent stimulation depends on the interval of signaling quiescence. For shorter intervals of signaling quiescence, the second response is blunted relative to the first response, whereas longer intervals of quiescence induce an enhanced second response. Through an iterative process of computational modeling and experimental tests, we found that these memory-like phenomena arise from a confluence of rapid, short-lived positive signals driven by the protein tyrosine kinase Syk; slow, long-lived negative signals driven by the lipid phosphatase Ship1; and slower degradation of Ship1 co-factors. This work advances our understanding of mast cell signaling and represents a generalizable approach for investigating the dynamics of signaling systems.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Carbonate clumped isotope analysis (Δ 47 ) of 21 carbonate standards determined via gas‐source isotope‐ratio mass spectrometry on four instrumental configurations using carbonate‐based standardization and multiyear data sets

Rationale Clumped isotope geochemistry examines the pairing or clumping of heavy isotopes in molecules and provides information about the thermodynamic and kinetic controls on their formation. The first clumped isotope measurements of carbonate minerals were first published 15 years ago, and since then, interlaboratory offsets have been observed, and laboratory and community practices for measurement, data analysis, and instrumentation have evolved. Here we briefly review historical and recent developments for measurements, share Tripati Lab practices for four different instrument configurations, test a recently published proposal for carbonate‐based standardization on multiple instruments using multi‐year data sets, and report values for 21 different carbonate standards that allow for recalculations of previously published data sets. Methods We examine data from 4628 standard measurements on Thermo MAT 253 and Nu Perspective IS mass spectrometers, using a common acid bath (90°C) and small‐sample (70°C) individual reaction vessels. Each configuration was investigated by treating some standards as anchors (working standards) and the remainder as unknowns (consistency standards). Results We show that different acid digestion systems and mass spectrometer models yield indistinguishable results when instrument drift is well characterized. For linearity correction, mixed gas‐and‐carbonate standardization or carbonate‐only standardization yields similar results. No difference is observed in the use of three or eight working standards for the construction of transfer functions. Conclusions We show that all configurations yield similar results if instrument drift is robustly characterized and validate a recent proposal for carbonate‐based standardization using large multiyear data sets. Δ 47 values are reported for 21 carbonate standards on both the absolute reference frame (ARF; also refered to as the Carbon Dioxide Equilibrated Scale or CDES) and the new InterCarb‐Carbon Dioxide Equilibrium Scale (I‐CDES) reference frame, facilitating intercomparison of data from a diversity of labs and instrument configurations and restandardization of a broad range of sample sets between 2006, when the first carbonate measurements were published, and the present.

58 GEOSCIENCES↗
DOE OSTI2021

Tank Side Cesium Removal IXC-150 Cask Detonation Report

A set of experiments were conducted at Los Alamos National Laboratory’s firing point 88 to determine the blast pressure and effects of a stoichiometric gas mixture of Hydrogen (H 2 ) and Nitrous Oxide (N 2 O) on the IXC-150 Storage Pad Vent Stack assemblies. The Lab was asked to design, build, and test the vent stack assemblies using a reaction gas volume of 340 in 3 that mimics the Tank Side Cesium Removal (TSCR) Ion Exchange Column (IXC) assembly. The experimental system with vent stack assembly was designed with input from the Washington River Protection Services (WRPS) to ensure an accurate test setup. The tests were conducted at LANL on the newly built filter/gas assembly at the end of April 2021 timeframe, using WRPS supplied vent stack assemblies and internal HEPA filters. The objective of these tests was to observe that the structural integrity of the vent stack assemblies was maintained and determine the resulting blast overpressures at a distance of 16 and 32 inches from the assembly. All work was performed under the LANL Quality Assurance Program (SD330), using a graded application of ASME NQA-1- 2008/NQA-1a-2009. To ensure that all client quality assurance (QA) expectations were addressed, evaluation of the end data needs was performed and the appropriate controls applied for this work.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks

Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. In this work, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal–organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal–organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Lastly and most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Revealing multiscale competing processes in the solid-state synthesis of single-crystalline layered oxide positive electrodes

Solid-state synthesis involves a web of coupled chemical reactions and physical changes that unfold across multiple scales. Efforts to fine-tune its parameters have historically followed heuristic, trial-driven workflows that demand significant time and resources. In this study, we aimed to open this black box by employing multiscale in situ synchrotron imaging and diffraction. Using LiNi 0.5 Mn 0.3 Co 0.2 O 2 battery positive electrode material as a model system and Ba-based sintering aids, we reveal dopant segregation, intergranular mass transport, and porosity evolution as key drivers of single-crystalline particle formation. Notably, we uncovered a dynamic competition between particle-level grain coalescence and atomic-scale cation disordering, both of which are thermally activated yet have opposing impacts on battery performance. These findings highlight the coupled, multiscale nature of structure development and offer a mechanistic basis for optimizing the solid-state synthesis process. This framework provides a path toward more controlled, efficient, and scalable production of high-performance battery positive electrode materials.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Future of Electron Scattering and Diffraction

The ability to correlate the atomic- and nanoscale-structure of condensed matter with physical properties (e.g., mechanical, electrical, catalytic, and optical) and functionality forms the core of many disciplines. Directing and controlling materials at the quantum-, atomic-, and molecular-levels creates enormous challenges and opportunities across a wide spectrum of critical technologies, including those involving the generation and use of energy. The workshop identified next generation electron scattering and diffraction instruments that are uniquely positioned to address these grand challenges. The workshop participants identified four key areas where the next generation of such instrumentation would have major impact: A – Multidimensional Visualization of Real Materials B – Atomic-scale Molecular Processes C – Photonic Control of Emergence in Quantum Materials D – Evolving Interfaces, Nucleation, and Mass Transport Real materials are comprised of complex three-dimensional arrangements of atoms and defects that directly determine their potential for energy applications. Understanding real materials requires new capabilities for three-dimensional atomic scale tomography and spectroscopy of atomic and electronic structures with unprecedented sensitivity, and with simultaneous spatial and energy resolution. Many molecules are able to selectively and efficiently convert sunlight into other forms of energy, like heat and electric current, or store it in altered chemical bonds. Understanding and controlling such process at the atomic scale require unprecedented time resolution. One of the grand challenges in condensed matter physics is to understand, and ultimately control, emergent phenomena in novel quantum materials that necessitate developing a new generation of instruments that probe the interplay among spin, charge, orbital, and lattice degrees of freedom with intrinsic time- and length-scale resolutions. Molecules and soft matter require imaging and spectroscopy with high spatial resolution without damaging their structure. The strong interaction of electrons with matter allows high-energy electron pulses to gather structural information before a sample is damaged. Electron ScatteringImaging, diffraction, and spectroscopy are the fundamental capabilities of electron-scattering instruments. The DOE BES-funded TEAM (Transmission Electron Aberration-corrected Microscope) project achieved unprecedented sub-atomic spatial resolution in imaging through aberration-corrected transmission electron microscopy. To further advance electron scattering techniques that directly enable groundbreaking science, instrumentation must advance beyond traditional two-dimensional imaging. Advances in temporal resolution, recording the full phase and energy spaces, and improved spatial resolution constitute a new frontier in electron microscopy, and will directly address the BES Grand Challenges, such as to “control the emergent properties that arise from the complex correlations of atomic and electronic constituents” and the “hidden states” “very far away from equilibrium”. Ultrafast methods, such as the pump-probe approach, enable pathways toward understanding, and ultimately controlling, the chemical dynamics of molecular systems and the evolution of complexity in mesoscale and nanoscale systems. Central to understanding how to synthesize and exploit functional materials is having the ability to apply external stimuli (such as heat, light, a reactive flux, and an electrical bias) and to observe the resulting dynamic process in situ and in operando, and under the appropriate environment (e.g., not limited to UHV conditions). To enable revolutionary advances in electron scattering and science, the participants of the workshop recommended three major new instrumental developments: A. Atomic-Resolution Multi-Dimensional Transmission Electron Microscope: This instrument would provide quantitative information over the entire real space, momentum space, and energy space for visualizing dopants, interstitials, and light elements; for imaging localized vibrational modes and the motion of charged particles and vacancies; for correlating lattice, spin, orbital, and charge; and for determining the structure and molecular chemistry of organic and soft matter. The instrument will be uniquely suited to answer fundamental questions in condensed matter physics that require understanding the physical and electronic structure at the atomic scale. Key developments include stable cryogenic capabilities that will allow access to emergent electronic phases, as well as hard/soft interfaces and radiation- sensitive materials. B. Ultrafast Electron Diffraction and Microscopy Instrument: This instrument would be capable of nano-diffraction with 10 fs temporal resolution in stroboscopic mode, and better than 100 fs temporal resolution in single shot mode. The instrument would also achieve single- shot real-space imaging with a spatial/temporal resolution of 10 nm/10 ps, representing a thousand fold improvement over current microscopes. Such a capability would be complementary to x-ray free electron lasers due to the difference in the nature of electron and x-ray scattering, enabling space-time mapping of lattice vibrations and energy transport, facilitating the understanding of molecular dynamics of chemical reactions, the photonic control of emergence in quantum materials, and the dynamics of mesoscopic materials. C. Lab-In-Gap Dynamic Microscope: This instrument would enable quantitative measurements of materials structure, composition, and bonding evolution in technologically relevant environments, including liquids, gases and plasmas, thereby assuring the understanding of structure function relationship at the atomic scale with up to nanosecond temporal resolution. This instrument would employ a versatile, modular sample stage and holder geometry to allow the multi-modal (e.g., optical, thermal, mechanical, electrical, and electrochemical) probing of materials’ functionality in situ and in operando. The electron optics encompasses a pole piece that can accommodate the new stage, differential pumping, detectors, aberration correctors, and other electron optical elements for measurement of materials dynamics. To realize the proposed instruments in a timely fashion, BES should aggressively support research and development of complementary and enabling instruments, including new electron sources, advanced electron optics, new tunable specimen pumps and sample stages, and new detectors. The proposed instruments would have transformative impact on physics, chemistry, materials science, engineering

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

State predictive information bottleneck

We report the ability to make sense of the massive amounts of high-dimensional data generated from molecular dynamics simulations is heavily dependent on the knowledge of a low-dimensional manifold (parameterized by a reaction coordinate or RC) that typically distinguishes between relevant metastable states, and which captures the relevant slow dynamics of interest. Methods based on machine learning and artificial intelligence have been proposed over the years to deal with learning such low-dimensional manifolds, but they are often criticized for a disconnect from more traditional and physically interpretable approaches. To deal with such concerns, in this work we propose a deep learning based state predictive information bottleneck approach to learn the RC from high-dimensional molecular simulation trajectories. We demonstrate analytically and numerically how the RC learnt in this approach is connected to the committor in chemical physics and can be used to accurately identify transition states. A crucial hyperparameter in this approach is the time delay or how far into the future the algorithm should make predictions about. Through careful comparisons for benchmark systems, we demonstrate that this hyperparameter choice gives useful control over how coarse-grained we want the metastable state classification of the system to be. We thus believe that this work represents a step forward in systematic application of deep learning based ideas to molecular simulations.

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

N2-to-NH3 conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

Ammonia (NH 3 ) is one of the basic chemicals in artificial fertilizers and a promising carbon-free energy storage carrier. Its industrial synthesis is typically realized via the Haber−Bosch process using traditional iron-based catalysts. Developing advanced catalysts that can reduce the N 2 activation barrier and make NH 3 synthesis more efficient is a long-term goal in the field. Most heterogeneous catalysts for N 2 -to-NH 3 conversion are multicomponent systems with singly dispersed metal clusters on supporting materials to activate N 2 and H 2 molecules. Herein, we report single-component heterogeneous catalysts based on 5 f actinide dioxide surfaces (ThO 2 and UO 2 ) with oxygen vacancies for N 2 -to-NH 3 conversion. The reaction cycle we propose is enabled by a dual-site mechanism, where N 2 and H 2 can be activated at different vacancy sites on the same surface; NH 3 is subsequently formed by H − migration on the surface via associative pathways. Oxygen vacancies recover to their initial states after the release of two molecules of NH 3 , making it possible for the catalytic cycle to continue. Our work demonstrates the catalytic activities of oxygen vacancies on 5 f actinide dioxide surfaces for N 2 activation, which may inspire the search for highly efficient, single-component catalysts that are easy to synthesize and control for NH 3 conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Radiation-Induced Plutonium Redox Chemistry

Plutonium plays a key role in global actinide research and nuclear fuel cycle technologies, and yet, our fundamental understanding of its inherent radiation-induced chemical behavior is limited. These radiation-induced processes cannot simply be switched off, as they are as fundamentally inherent to plutonium as the impact of relativistic effects on its f-electrons. In less chemically complex actinide systems, such as aqueous solutions of neptunium and americium, , radiolysis products play a significant role in the redox cycling of their oxidation states. However, plutonium's multiple, coexisting, and chemically active oxidation states, which comprise of bare ions and dioxo cations, provide additional redox pathways that complicate radiation-induced processes. Oxidation state control is critical for the manipulation of plutonium, especially in used nuclear fuel reprocessing technologies, where oxidation specific states are successfully extracted, and others rejected. Consequently, mechanistically understanding the behavior of plutonium’s multiple oxidation states in the presence of intense ionizing radiation fields is essential for predicting the behavior of this element under multiple conditions that support the development and innovation of nuclear fuel cycle technologies. Here, we present recent advances in our understanding of plutonium radiation chemistry, including the first-ever multiscale model for predicting gamma radiation-induced plutonium redox chemistry, and new chemical kinetics for the reaction of plutonium and its complexes of tributyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) with transients radiolysis products, a measured using electron pulse radiolysis.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Redox-Induced Microstructure and Phase Dynamics in Nickel: Insights from In Situ Synchrotron X-ray Diffraction

Using in situ synchrotron X-ray diffraction, we interrogate the microstructural and phase evolution of polycrystalline nickel (Ni) during redox cycling in O 2 , H 2 , and H 2 O environments. Oxidation in O 2 promotes strong (111) texturing in both the NiO overlayer and the underlying Ni substrate. However, this crystallographic alignment is lost following reduction in H 2 and subsequent reoxidation, demonstrating irreversible microstructural changes. H 2 exposure leads to proton dissolution into the Ni lattice, triggering a localized phase transition from face-centered cubic (FCC) to hexagonal close-packed (HCP) Ni in hydrogen-saturated regions. In H 2 O-containing atmospheres, dissociative H 2 O adsorption produces protons that permeate the NiO layer, forming γ-NiOOH within the NiO lattice and HCP Ni beneath the NiO overlayer as protons accumulate. Kinetic analysis via the Johnson-Mehl-Avrami–Kolmogorov model uncovers distinct growth mechanisms: preoxidized Ni surfaces follow one-dimensional (1D) kinetics for NiO, γ-NiOOH, and HCP growth, whereas pristine Ni exhibits three-dimensional (3D) kinetics due to island-like nucleation and growth of NiO. Furthermore, these results highlight the critical interplay between H 2 O dissociation, hydrogen permeation, and redox-driven phase transformations, with practical implications in engineering nickel-based catalysts and hydrogen storage systems through controlled microstructural and phase evolution.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Acyl-chain remodeling of dioctanoyl-phosphatidylcholine in Saccharomyces cerevisiae mutant defective in de novo and salvage phosphatidylcholine synthesis

Highlights: • Dioctanoyl-PC (diC8PC) supported growth of a yeast mutant defective in PC synthesis. • diC8PC was converted to PC species containing longer acyl residues in the mutant. • Both acyl residues of diC8PC were replaced by longer fatty acids in vitro. • This system will contribute to the elucidation of the acyl chain remodeling of PC. - Abstract: A yeast strain, in which endogenous phosphatidylcholine (PC) synthesis is controllable, was constructed by the replacement of the promoter of PCT1, encoding CTP:phosphocholine cytidylyltransferase, with GAL1 promoter in a double deletion mutant of PEM1 and PEM2, encoding phosphatidylethanolamine methyltransferase and phospholipid methyltransferase, respectively. This mutant did not grow in the glucose-containing medium, but the addition of dioctanoyl-phosphatidylcholine (diC8PC) supported its growth. Analyses of the metabolism of {sup 13}C-labeled diC8PC ((methyl-{sup 13}C){sub 3}-diC8PC) in this strain using electrospray ionization tandem mass spectrometry revealed that it was converted to PC species containing acyl residues of 16 or 18 carbons at both sn-1 and sn-2 positions. In addition, both acyl residues of (methyl-{sup 13}C){sub 3}-diC8PC were replaced with 16:1 acyl chains in the in vitro reaction using the yeast cell extract in the presence of palmitoleoyl-CoA. These results indicate that PC containing short acyl residues was remodeled to those with acyl chains of physiological length in yeast.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Contact with Electrically Conductive Inert Solids Alters Intrinsic Heterogeneous Brønsted Acid Catalysis

Interfacial electric fields at heterogeneous catalyst surfaces have been demonstrated to alter kinetics of liquid-phase reactions. In these systems, electric fields are generated from applying a potential to the catalyst through connection to a potentiostat or through electron transfer from redox-active species in solution. Here, we demonstrate that catalyst polarization can also occur by simply contacting electrically conductive inert solids, leading to the counterintuitive conclusion that a catalyst particle touching an inert solid can alter intrinsic reaction rates. Using dehydration of 1-methylcyclopentanol to 1-methylcyclopentene catalyzed by Brønsted-acidic carboxylic acid groups on carbon nanotubes as a proof-of-concept probe reaction, we show that catalyst contact with inert, thermally reduced carbon nanotubes leads to order-of-magnitude changes in reaction rate. Furthermore, we demonstrate that these contact-induced effects can also be observed under standard laboratory reaction conditions, where particle-to-particle contact in stirred catalyst powder suspensions is sufficient to demote rates by ∼8-fold. This work provides the foundation for a new method of reaction rate control, which could have implications whenever heterogeneous catalyst particles are in contact with inert materials for liquid-phase reactions in the presence of electrolyte.

Alcohols↗
DOE OSTI2016

Proton Minibeam Radiation Therapy Reduces Side Effects in an In Vivo Mouse Ear Model

Purpose: Proton minibeam radiation therapy is a novel approach to minimize normal tissue damage in the entrance channel by spatial fractionation while keeping tumor control through a homogeneous tumor dose using beam widening with an increasing track length. In the present study, the dose distributions for homogeneous broad beam and minibeam irradiation sessions were simulated. Also, in an animal study, acute normal tissue side effects of proton minibeam irradiation were compared with homogeneous irradiation in a tumor-free mouse ear model to account for the complex effects on the immune system and vasculature in an in vivo normal tissue model. Methods and Materials: At the ion microprobe SNAKE, 20-MeV protons were administered to the central part (7.2 × 7.2 mm{sup 2}) of the ear of BALB/c mice, using either a homogeneous field with a dose of 60 Gy or 16 minibeams with a nominal 6000 Gy (4 × 4 minibeams, size 0.18 × 0.18 mm{sup 2}, with a distance of 1.8 mm). The same average dose was used over the irradiated area. Results: No ear swelling or other skin reactions were observed at any point after minibeam irradiation. In contrast, significant ear swelling (up to fourfold), erythema, and desquamation developed in homogeneously irradiated ears 3 to 4 weeks after irradiation. Hair loss and the disappearance of sebaceous glands were only detected in the homogeneously irradiated fields. Conclusions: These results show that proton minibeam radiation therapy results in reduced adverse effects compared with conventional homogeneous broad-beam irradiation and, therefore, might have the potential to decrease the incidence of side effects resulting from clinical proton and/or heavy ion therapy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2021

Methane generation from low-maturity coals and shale source rocks at low temperatures (80–120 °C) over 14–38 months

This study contributes long-term (14 to 38 months) experimental evidence for geocatalytically mediated methanogenesis in immature to early mature shale and coal source rocks at temperatures from 80 to 120 °C. Borosilicate glass tubes with pre-outgassed coal and shale source rock chips and water were sealed under vacuum, sterilized, heated isothermally, and finally opened in connection with a vacuum line where headspace gases methane (CH 4 ) and carbon dioxide (CO 2 ) were collected. The possibility of admitting pre-existing CH 4 from closed pores into product gases during heating experiments was evaluated by comparative ball milling of original and heated rock chips, followed by quantitation of released gases with a novel closed-circuit laser-based SARAD RTM2200 gas detector system with sub-µmol sensitivity. The yields of produced CH 4 from individual source rocks were corrected by subtracting the amounts of pre-existing CH 4 from formerly closed pores in original source rocks that had leaked during long-term heating. Different shales and coals express contrasting propensities to geocatalytically generate CH 4 and CO 2 , with CH 4 yields ranging from 0.1 to 5.5 µmol g-1 total organic carbon (TOC). CH 4 yields from two petrographically different samples of Springfield Coal with comparable thermal maturity suggest that liptinite expresses a far higher propensity for methanogenesis, but liberates less CO 2 than vitrinite. Shale from the Second White Specks Formation generated approximately 10 times more CH 4 than New Albany Shale per g of TOC, further suggesting complex controls on CH 4 generation during catalytic methanogenesis. Higher temperature can enhance the activities of catalytic methanogenesis. Here, the extrapolation of laboratory-based reaction rates to natural conditions in organic-rich buried sediments suggests that geocatalytic methanogenesis can be fast enough in some source rocks to generate economically sizeable gas plays from immature to early mature source rocks over geologic time.

03 NATURAL GAS↗
DOE OSTI2014

How to Chemically Tailor Metal-Porphyrin-Like Active Sites on Carbon Nanotubes and Graphene for Minimal Overpotential in the Electrochemical Oxygen Evolution and Oxygen Reduction Reactions

Density functional theory calculations are used to study the energetics of the electrochemical oxygen evolution reaction (OER) of water and the reverse oxygen reduction reaction (ORR) on metal-porphyrin-like centers incorporated into graphene layers or single-walled carbon nanotubes (SWCNTs). The objective is to explore the reductions in computational thermodynamic overpotential that can be achieved relative to catalysis on metal oxide surfaces (OER) or platinum (ORR) by varying the metal center and axial ligand. This permits a degree of simultaneous control over the free energy gap between the lowest energy OH and highest energy OOH intermediates, and the position of the oxo (O) intermediate in this gap. Optimal choice of metal toward the right of the first transition series largely controls the gap. Given a suitable metal such as Fe, the overpotential for OER can be tuned over a range greater than 0.35 V by choice of the axial ligand. For OER occurring within the SWCNTs, a minimum predicted overpotential of 0.35 V is found, very close to the gap-imposed limit of 0.30 V for this system. Similarly, the overpotential of ORR can be tuned over a range more than 0.30 V by selection of the axial ligand. While the calculations necessarily have limited accuracy, the principles should provide a transferable path toward overpotential optimization for the OER and ORR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗