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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

CO 2 Capture by Hybrid Ultramicroporous TIFSIX‐3‐Ni under Humid Conditions Using Non‐Equilibrium Cycling

Abstract Although pyrazine‐linked hybrid ultramicroporous materials (HUMs, pore size <7 Å) are benchmark physisorbents for trace carbon dioxide (CO 2 ) capture under dry conditions, their affinity for water (H 2 O) mitigates their carbon capture performance in humid conditions. Herein, we report on the co‐adsorption of H 2 O and CO 2 by TIFSIX‐3‐Ni—a high CO 2 affinity HUM—and find that slow H 2 O sorption kinetics can enable CO 2 uptake and release using shortened adsorption cycles with retention of ca. 90 % of dry CO 2 uptake. Insight into co‐adsorption is provided by in situ infrared spectroscopy and ab initio calculations. The binding sites and sorption mechanisms reveal that both CO 2 and H 2 O molecules occupy the same ultramicropore through favorable interactions between CO 2 and H 2 O at low water loading. An energetically favored water network displaces CO 2 molecules at higher loading. Our results offer bottom‐up design principles and insight into co‐adsorption of CO 2 and H 2 O that is likely to be relevant across the full spectrum of carbon capture sorbents to better understand and address the challenge posed by humidity to gas capture.

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

Revisiting Competing Paths in Electrochemical CO 2 Reduction on Copper via Embedded Correlated Wavefunction Theory

We re-evaluate two key steps in the mechanism of CO 2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. Here, we optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT’s inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) is to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO 2 reduction, which is the subject of ongoing work.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Electrical injection and transport in Teflon-diluted hole transport materials

Diluting small molecule organic semiconductor hole transport materials with Teflon AF (TAF) dramatically increases their thermal/morphological stability while counterintuitively also increasing the current density in hole-only diodes. Here, we explore the origin of this current enhancement in co-evaporated blends of TAF and N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD) and find that it results from improved hole injection and not from a mobility enhancement due to semiconductor dilution effects. Whereas electroabsorption measurements indicate that an interface dipole shift of up to 0.5 eV (depending on TAF concentration) aides hole injection at the indium-tin-oxide anode, time-of-flight and temperature-dependent current-voltage measurements show that the mobility of 25 vol% TAF:NPD blends decreases by roughly an order of magnitude relative to neat NPD despite having slightly lower energetic disorder. For comparison, diluting with 25 vol% high density polyethylene achieves a similar reduction in energetic disorder but only decreases the mobility by a factor of two. Furthermore, these results highlight the tradeoff between reducing energetic disorder and frustrating percolation in diluted organic semiconductors, and represent a step toward thermally-evaporated polymer-small molecule composites that maintain high mobility while offering improved morphological stability and lower refractive index for organic light emitting diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Emergent topological quasiparticle kinetics in constricted nanomagnets

The ubiquitous domain wall kinetics under magnetic field or current application describes the dynamic properties in nanostructured magnets. However, when the geometrical size of a nanomagnetic system is constricted to the limiting domain wall length scale, the competing energetics between anisotropy, exchange, and dipolar interactions can cause emergent kinetics due to quasiparticle relaxation, similar to bulk magnets of atomic origin. This paper presents a joint experimental and theoretical study to support this argument: constricted nanomagnets, made of antiferromagnetic and paramagnetic neodymium thin film with honeycomb motif, reveal fast kinetic events at picosecond timescales due to the relaxation of topological quasiparticles that persist to low temperature in the absence of any external stimuli. This discovery is especially important considering the fact that paramagnets or antiferromagnets have no net magnetization. Yet, the kinetics in neodymium nanostructures is quantitatively similar to that found in ferromagnetic counterparts and only varies with the thickness of the specimen. This suggests that a universal, topological quasiparticle-mediated dynamical behavior can be prevalent in nanoscopic magnets, irrespective of the nature of the underlying magnetic material.

Guo, Jiasen↗
DOE OSTI2025

Divertor Plasma Detachment Control Neural Network

DivControlNN is a state-of-the-art software tool that leverages advanced machine learning techniques to predict and control divertor plasma behavior in fusion reactors. Plasma, a highly energetic and electrically charged gas, requires meticulous management to protect reactor components and maintain optimal energy production. Conventional simulation methods, although extremely detailed, typically demand extensive computational time-making them unsuitable for real-time control scenarios. DivControlNN addresses this challenge by learning from tens of thousands of high-fidelity simulations, thereby creating a rapid surrogate model that can deliver near-instantaneous predictions. At the core of its functionality is a sophisticated technique known as latent space mapping, which condenses complex, high-dimensional plasma data into a compact, lower-dimensional representation. This streamlined representation enables the system to quickly forecast essential plasma properties and determine the precise conditions required for effective detachment. Detachment is a crucial process in which the plasma is cooled before reaching the divertor plates, thereby reducing heat loads and mitigating material erosion. In recent experiments conducted on the KSTAR tokamak in South Korea, DivControlNN successfully guided the detachment process without any fine-tuning-even when applied to a new tungsten divertor configuration. By achieving a computational speed-up of over one hundred million times compared to traditional simulation methods while maintaining low prediction errors, DivControlNN stands to significantly enhance real-time control and diagnostic capabilities in future fusion reactors. This breakthrough paves the way for safer, more reliable reactor operation and represents a major advancement toward realizing fusion energy as a practical, sustainable, and clean power source.

Xu, Xueqiao [Lawrence Livermore National Laborator↗
DOE OSTI2023

Defect Quantification in Metal Halide Perovskites Anticipates Photoluminescence and Photovoltaic Performance

Semiconductor material optimization requires quantification of performance and stability-dependent near-valence maximum and near-conduction minimum defects with sufficient energy resolution and sensitivity. In this work, we utilize a spectroscopy-electrochemistry approach to resolve the energy-distinct donor and acceptor defect concentrations in wide-gap (Cs .05 FA .79 MA .16 )Pb(I .87 Br .13 ) 3 perovskites, benchmarked against photoluminescence and photovoltaic device performance. Monitoring charge transfer events to electron acceptor and donor molecules within solid electrolyte top contacts enables defect quantification below 10 15 cm –3 at an energy resolution of 10 meV under device-relevant bias, well below levels reported by other methods. Further method sensitivity is demonstrated for defects arising from <2% formamidinium concentration modifications, mimicking compositional imperfections resulting from nonoptimized processing. This method provides the first complete perovskite energetic diagrams with small changes in composition, is nondestructive, compatible with in-line processing characterization, and will enable the semiconductor community to link molecular origins of defects with limitations in device performance across a wide array of optoelectronic platforms.

14 SOLAR ENERGY↗
DOE OSTI2022

Assessing the stability of Pd-exchanged sites in zeolites with the aid of a high throughput quantum chemistry workflow

Abstract Cation exchanged-zeolites are functional materials with a wide range of applications from catalysis to sorbents. They present a challenge for computational studies using density functional theory due to the numerous possible active sites. From Al configuration, to placement of extra framework cation(s), to potentially different oxidation states of the cation, accounting for all these possibilities is not trivial. To make the number of calculations more tractable, most studies focus on a few active sites. We attempt to go beyond these limitations by implementing a workflow for a high throughput screening, designed to systematize the problem and exhaustively search for feasible active sites. We use Pd-exchanged CHA and BEA to illustrate the approach. After conducting thousands of explicit DFT calculations, we identify the sites most favorable for the Pd cation and discuss the results in detail. The high throughput screening identifies many energetically favorable sites that are non-trivial. Lastly, we employ these results to examine NO adsorption in Pd-exchanged CHA, which is a promising passive NO x adsorbent (PNA) during the cold start of automobiles. The results shed light on critical active sites for NO x capture that were not previously studied.

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

Combining ToF‐SIMS and Multivariate Analysis to Resolve Active Sites on Ni‐Based HER Catalysts

Unambiguous identification of active sites in heterogeneous catalysis remains a major challenge, particularly for materials with ultrathin, chemically mixed surface layers. Here, we demonstrate a generalizable approach that combines time-of-flight secondary ion mass spectrometry (ToF-SIMS) with multivariate statistical analysis (principal component analysis [PCA] and multivariate curve resolution [MCR]) to resolve catalytically relevant motifs at the nanoscale. Using Ni electrodes as a model system, PCA distinguished hydroxide-enriched domains from oxide- and metal-rich regions, while MCR decomposed depth profiles and 3D images into hydroxide, oxide, and metallic layers with nanometer resolution. A unique secondary-ion fragment, NiO 3 H 3 − (m/z 108.94), emerged as a marker of hydroxide-rich environments and correlated with hydrogen evolution reaction (HER) activity across a series of Ni electrodes. Complementary density functional theory (DFT) calculations revealed that Ni(OH) 2 clusters adjacent to metallic Ni offer the most favorable water dissociation energetics, establishing the structural origin of the marker. While illustrated here for Ni-based HER, this workflow provides a broadly applicable framework to isolate and rank near-surface patterns that govern catalytic activity, thereby extending ToF-SIMS from a qualitative probe to a predictive tool for active site identification.

HER active sites↗
DOE OSTI2020

Magnetically driven phonon instability enables the metal–insulator transition in h-FeS

Hexagonal iron sulfide exhibits a fascinating coexistence of metal–insulator, structural and magnetic transitions, reflecting an intimate interplay of its spin, phonon and charge degrees of freedom. Here, we show how a subtle competition of energetic and entropic free-energy components governs its thermodynamics and the sequence of phase transitions it undergoes upon cooling. By means of comprehensive neutron and X-ray scattering measurements, and supported by first-principles electronic structure simulations, we identify the critical role of the coupling between antiferromagnetic ordering and instabilities of anharmonic phonons in the metallic phase in driving the metal–insulator transition. The antiferromagnetic ordering enables the emergence of two zone-boundary soft phonons, whose coupling to a zone-centre mode drives the lattice distortion opening the electronic bandgap. Simultaneously, spin–lattice coupling opens a gap in the magnon spectrum that controls the entropy component of the metal–insulator transition free energy. Furthermore, these results reveal the importance of spin–phonon coupling to tune anharmonic effects, thus opening new avenues to design novel technologically important materials harbouring the metal–insulator transition and magnetoelectric behaviours.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Stabilizing the crystal structures of NaFePO 4 with Li substitutions

Due to the high cost and insufficient resources of lithium, alternative sodium-ion batteries have been widely investigated for large-scale applications. NaFePO 4 has the highest theoretical capacity of 154 mA h g -1 among the iron-based phosphates, which makes it an attractive cathode material for Na-ion batteries. Experimentally, LiFePO 4 has been highly successful as a cathode material in Li-ion batteries because its olivine crystal structure provides a stable framework during battery cycling. In NaFePO 4 , maricite replaces olivine as the most stable phase. However, the maricite phase is experimentally found to be electrochemically inactive under normal battery operating voltages (0–4.5 V). We found that partial substitutions of Na with Li stabilize the olivine structure and may be a way to improve the performance of NaFePO 4 cathodes. Using the previously developed structural LiFePO 4 database, here we examine the low-energy crystal structures in the system when we replace Li with Na. The known maricite and olivine NaFePO 4 phases are reconfirmed and an unreported phase with energy between them is identified by our calculations. Besides, the Li-doped olivine type compound Li x Na 1- x FePO 4 with mixed alkali ions retains better energetic stability compared with the other two types of structures of the same composition, as long as the proportion of Li exceeds 0.25. The thermodynamic stability of o-type Li x Na 1- x FePO 4 can be further improved at finite temperatures. The primary limitation of the calculations is that we mainly focus on the zero-temperature condition; however, the relative stability of the structures may vary depending on the ambient temperature.

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

Discovery, Timing, and Multiwavelength Observations of the Black Widow Millisecond Pulsar PSR J1555–2908

Abstract We report the discovery of PSR J1555−2908, a 1.79 ms radio and gamma-ray pulsar in a 5.6 hr binary system with a minimum companion mass of 0.052 M ⊙ . This fast and energetic ( E ̇ = 3 × 10 35 erg s −1 ) millisecond pulsar was first detected as a gamma-ray point source in Fermi Large Area Telescope (LAT) sky survey observations. Guided by a steep-spectrum radio point source in the Fermi error region, we performed a search at 820 MHz with the Green Bank Telescope that first discovered the pulsations. The initial radio pulse timing observations provided enough information to seed a search for gamma-ray pulsations in the LAT data, from which we derive a timing solution valid for the full Fermi mission. In addition to the discovery and timing of radio and gamma-ray pulsations, we searched for X-ray pulsations using NICER but no significant pulsations were detected. We also obtained time-series r -band photometry that indicates strong heating of the companion star by the pulsar wind. Material blown off the heated companion eclipses the 820 MHz radio pulse during inferior conjunction of the companion for ≈10% of the orbit, which is twice the angle subtended by its Roche lobe in an edge-on system.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

On the Dynamics of the Carbon–Bromine Bond Dissociation in the 1-Bromo-2-Methylnaphthalene Radical Anion

This paper studies the mechanism of electrochemically induced carbon–bromine dissociation in 1-Br-2-methylnaphalene in the reduction regime. In particular, the bond dissociation of the relevant radical anion is disassembled at a molecular level, exploiting quantum mechanical calculations including steady-state, equilibrium and dissociation dynamics via dynamic reaction coordinate (DRC) calculations. DRC is a molecular-dynamic-based calculation relying on an ab initio potential surface. This is to achieve a detailed picture of the dissociation process in an elementary molecular detail. From a thermodynamic point of view, all the reaction paths examined are energetically feasible. The obtained results suggest that the carbon halogen bond dissociates following the first electron uptake follow a stepwise mechanism. Indeed, the formation of the bromide anion and an organic radical occurs. The latter reacts to form a binaphthalene intrinsically chiral dimer. This paper is respectfully dedicated to Professors Anny Jutand and Christian Amatore for their outstanding contribution in the field of electrochemical catalysis and electrosynthesis.

1-bromo-2-methylnaphthalene↗
DOE OSTI2020

Chapter 8. Hybrid Biological–Inorganic Systems for CO 2 Conversion to Fuels

The biological reduction of CO 2 into organic carbon is integral to the formation and maintenance of all life on earth. An urgent need to mitigate the effects of CO 2 on our atmosphere has provided an imperative to exploit biological CO 2 fixation for the conversion of CO2 into valuable and energy rich fuels. Photosynthesis uses only sunlight, water, and CO2 as starting materials to form all biomass.

CO2 Conversion to Fuels↗
DOE OSTI2024

Precision Calcination Mechanism of CaCO 3 to High-Porosity Nanoscale CaO CO 2 Sorbent Revealed by Direct In Situ Observations

Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO 3 to CaO and CO 2 , and the rapid loss of CO 2 absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO 3 decomposition reaction pathway requires direct observation by time-resolved (sub-)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO 3 nanoparticles to nanoporous CaO particles comprising high-surface-area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X-ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO 3 thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time-resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO 3 defects followed by sweeping reaction front motion across the initial CaCO 3 particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub-)nanoscale dynamics, while also demonstrating calcination of CaCO 3 without sintering through rapid heating and precise temperature control.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Simultaneous Improvements in Efficiency and Stability of Organic Solar Cells via a Symmetric‐Asymmetric Dual‐Acceptor Strategy

Abstract Simultaneously achieving improvements in power conversion efficiency (PCE) and stability is the main task of the current development stage of organic solar cells (OSCs). This work reports a symmetry–asymmetry dual‐acceptor (SADA) strategy to construct ternary devices, which is found to be feasible for increasing both the PCE and the operational lifetime of OSCs. In this contribution, the symmetric acceptor L8‐BO and the asymmetric acceptor BTP‐S9 are blended in equal proportions with polymer donor PM6 for the consideration of absorption spectrum complementarity and cascade energetic alignment. In addition, the features of crystallinity and miscibility of the dual‐acceptor deliver optimized morphology lead to a high PCE of 18.84%. In addition, the asymmetric acceptor BTP‐S9 with a larger dipole moment shows tighter molecular stacking and longer crystal correlation length, which favor intrinsic molecular photostability, and further consolidate the operational lifetime of OSCs when coordinated with L8‐BO. This work demonstrates the efficacy of the SADA strategy for constructing efficient and stable OSCs.

Chemistry↗
DOE OSTI2021

Tailoring Interfaces in Solid-State Batteries Using Interfacial Thermochemistry and Band Alignment

Solid-state lithium ion batteries have enhanced thermal stability compared to batteries using liquid electrolytes. Although their practical implementation is limited by undesired side reactions between the electrode and electrolyte, different modification strategies have been proposed to stabilize these reactive interfaces. These approaches have been primarily based upon bulk materials properties, however, which may not necessarily be representative of the chemistry at the solid/solid interface. In this work, first principles calculations and X-ray scattering experiments are used to elucidate molecular-level reactivity and develop design principles for tailored interfaces based on surface and interfacial properties. Because of its well-known instability, the interface between the Li metal anode and the lithium lanthanum titanate (LLTO) solid electrolyte is applied as a model system. Density functional theory calculations are used to describe bulk, surface, and interfacial thermochemistry of the Li/LLTO system, and interfacial reconstruction is probed using ab initio molecular dynamics. These simulations of the Li/LLTO interface demonstrate facile decomposition concomitant with reduction of Ti 4+ ions. Based on further insights from computational analysis of the surface band edge positions, La 2 O 3 is proposed as an interlayer coating and is shown to provide an energetic barrier for interfacial charge transfer and decomposition reactions from X-ray reflectivity measurements and theoretical calculations. The findings in this work suggest that design strategies based on surface and interfacial properties can be used to kinetically stabilize electrode/electrolyte interfaces in solid-state batteries.

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

Unveiling the Emergent Traits of Chiral Spin Textures in Magnetic Multilayers

Abstract Magnetic skyrmions are topologically wound nanoscale textures of spins whose ambient stability and electrical manipulation in multilayer films have led to an explosion of research activities. While past efforts focused predominantly on isolated skyrmions, recently ensembles of chiral spin textures, consisting of skyrmions and magnetic stripes, are shown to possess rich interactions with potential for device applications. However, several fundamental aspects of chiral spin texture phenomenology remain to be elucidated, including their domain wall (DW) structure, thermodynamic stability, and morphological transitions. Here the evolution of these textural characteristics are unveiled on a tunable multilayer platform—wherein chiral interactions governing spin texture energetics can be widely varied—using a combination of full‐field electron and soft X‐ray microscopies with numerical simulations. With increasing chiral interactions, the emergence of Néel helicity, followed by a marked reduction in domain compressibility, and finally a transformation in the skyrmion formation mechanism are demonstrated. Together with an analytical model, these experiments establish a comprehensive microscopic framework for investigating and tailoring chiral spin texture character in multilayer films.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High-Temperature Observation of Intralayer, Interlayer, and Rydberg Excitons in Bulk Van Der Waals Alloy Single Crystals

Transition metal dichalcogenides exhibit remarkable optical properties due to the diverse number of strongly bound excitons, which can be fine-tuned by alloying. Despite a flurry of research activity in characterizing these excitons, a comprehensive and profound understanding of their behavior with temperature is lacking. Here, we report the rich spectrum of excitonic features within bulk van der Waals alloy Mo0.5 W0.5 S2 and Mo0.5 W0.5 Se2 single crystals through temperature-dependent reflectance spectroscopy and first-principles calculations. We observed Rydberg excitons and interlayer excitons in both the single crystals. Notably, we provide the first experimental evidence of highly energetic A' and B' excitons in Mo0.5 W0.5 S2 at room temperature. The strong carrier-phonon scattering significantly broadens the A', B', and interlayer excitons at room temperature in bulk Mo0.5 W0.5 S2 single crystal compared to its selenide. Our findings, supported by density functional theory and Bethe-Salpeter equation calculations, signify the crucial role of carrier-phonon interactions. These results open pathways for next-generation optoelectronic devices and quantum technologies operating at high temperature.

excitons↗