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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Polar primary aerosols across the ocean-sea ice-snow-atmosphere interface: From sources to impacts

Primary aerosols play a critical role in polar climate systems, influencing cloud formation, precipitation, radiative balance, and surface energy budgets. This paper provides a comprehensive synthesis of primary aerosol sources, transformation and removal processes, and broader atmospheric impacts in polar regions, emphasizing their links to ocean and sea ice biogeochemistry. These aerosols (including sea salt, primary organic aerosol, and primary biological aerosol particles) originate from marine and cryospheric environments and are emitted through physical processes, such as wave breaking, bubble bursting, and blowing snow. Emission sources include seawater, sea ice, snow, and freshwater from river discharge and glacial runoff. Once airborne, these particles can serve as a chemical reservoir, influencing atmospheric composition and reactivity, and as seeds for cloud droplet and ice crystal formation, influencing cloud microphysics and polar climate. Despite their importance, many of the processes governing primary aerosol emissions and transformations remain poorly constrained. The most pressing knowledge gaps pertain to emission processes, limited spatiotemporal observational coverage, instrumentation constraints, parameterization development, and the integration of interdisciplinary expertise. To improve our understanding of primary aerosol drivers and their response to climate, future research efforts should prioritize strategically coordinated and cross-disciplinary process studies, advancements in measurement technologies and coverage, and close collaboration between modelers and observational scientists to inform and refine model parameterizations. As polar regions continue to undergo profound changes marked by increased precipitation, reduced sea and land ice, freshening oceans, and shifting ecosystem dynamics, characterizing present-day primary aerosol populations is vital. Improved understanding will be essential for anticipating future changes in aerosol-radiation and aerosol-cloud interactions and their implications for polar and global climate systems.

Aerosol-cloud↗
DOE OSTI2024

Effects of Interactions Between Produced Formation Fluid and Rock Matrix on Pore Structure of Caney Shale, Southern Oklahoma

ABSTRACT: Rock-fluid interactions change properties of shales during exploitation. To investigate effects of rock-fluid interactions on pore structure of shales matrix after hydraulic fracturing, powder samples from two late Mississippian Caney Shale cores in the Ardmore Basin, southern Oklahoma, were used to react with formation produced fluid from the field in the batch reactor analysis. X-ray diffraction for mineralogy and Low-pressure nitrogen adsorption isotherms for pore structure were measured for original, after-7days, and after-30days samples. Results show that the samples consist mainly of quartz, followed by clay minerals, carbonates, and feldspar. The pore sizes of micropore (<2 nm) and mesopore (2-50 nm) increase 14%-233% due to dissolution of pyrite, feldspar, and carbonates after 7 days. Due to the transformation from smectite to illite and the increase of pore size, the specific surface area (SSA) decreases after 7-days interactions. After 30-days interactions, the micropore volume slightly increases and the mesopore and macropore volume decreases. Due to the decrease of pore size, the SSA of 30-days reacted samples increases correspondingly and is lower (for the clay-rich sample) or higher (for the calcareous sample) than that of the unreacted samples. Findings improve our understanding of dynamic alteration of shale properties during production. 1. INTRODUCTION Energy demand will continuously grow owing to the increasing global population as well as energy consumption (EIA, 2023). On the other hand, shale gas and oil reshaped the energy market in the United States, enabling the United States to become a net-export of natural gas country in 2017 (EIA, 2023). However, shale reservoirs are challenging tight formations that are still poorly understood in the extraction and production of hydrocarbons (Ross and Bustin, 2009; Curtis et al., 2012; Xiong et al., 2015, 2021a; Li Y. et al., 2016; Gong et al., 2019a; Benge et al., 2021; Awejori et al., 2022; Huang et al., 2022). One of the most challenging topics is the rock-fluid interactions post hydraulic fracturing and its subsequent impacts on the pore structures of fractured formation matrix.

Xiong, Fengyang↗
DOE OSTI2020

Structural phase transition and manifestation of eddy currents in IR reflection spectra of PbSnTe semiconductor films

Infrared reflection spectra of thin (∼60 nm) Pb{sub 1−x} Sn{sub x}Te (x = 0.25, 0.53, 0.59) films grown by molecular beam epitaxy on GaAs/CdTe hybrid substrates have been measured at frequencies from 20 to 5500 cm{sup −1} and temperatures from 5 to 300 K. The spectra have been used to determine temperature-dependent transverse phonon and plasmon frequencies in the films, which has made it possible to identify a structural phase transition at T{sub C} ≈ 50 K. The plasma frequency of the films has been shown to increase with decreasing band gap on cooling from 300 to 77 K. The increase in plasma frequency is mainly attributable to the increase in carrier concentration and a transition of the carriers from vortex states on the film surface to the valence band. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Predicting Catalyst Surface Stability Under Reaction Conditions Using Deep Reinforcement Learning and Machine Learning Potentials

Catalysts are critical for most large-scale energy intensive chemical transformation processes, such as energy storage, liquid fuel production, and the formation of chemical building blocks. The catalyst composition, structure, and morphology impact the performance under reaction conditions and influences properties like activity and selectivity. Many industrial catalysts offer imperfect activity/selectivity, or contain expensive metals. Further, catalysts can deactivate over time as the morphology changes or harsh reactive environments alter the surface structure. Methods to automatically model and predict the kinetics of how catalyst surfaces will restructure would enable engineers to design around these challenges, improve performance, increase longevity. This project investigated a specific type of machine learning model, deep reinforcement learning, machine learning models to act as surrogates for the physical system, and compared the results of these approaches with a specialized high-throughput experimental synthesis and measurement platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Role of generic scale invariance in a Mott transition from a U(1) spin-liquid insulator to a Landau Fermi-liquid metal

Highlights: • We look at the role played by generic scale invariance (GSI) in the phase transition between a U(1) spin liquid and a Fermi liquid. • We identify dangerously irrelevant operators in the renormalization group transformation, involved with the GSI. • We highlight novel mean-field dynamics of this Mott quantum criticality, resulting from the GSI. We investigate the role of generic scale invariance in a Mott transition from a U(1) spin-liquid insulator to a Landau Fermi-liquid metal, where there exist massless degrees of freedom in addition to quantum critical fluctuations. Here, the Mott quantum criticality is described by critical charge fluctuations, and additional gapless excitations are U(1) gauge-field fluctuations coupled to a spinon Fermi surface in the spin-liquid state, which turn out to play a central role in the Mott transition. An interesting feature of this problem is that the scaling dimension of effective leading local interactions between critical charge fluctuations differs from that of the coupling constant between U(1) gauge fields and matter-field fluctuations in the presence of a Fermi surface. As a result, there appear dangerously irrelevant operators, which can cause conceptual difficulty in the implementation of renormalization group (RG) transformations. Indeed, we find that the curvature term along the angular direction of the spinon Fermi surface is dangerously irrelevant at this spin-liquid Mott quantum criticality, responsible for divergence of the self-energy correction term in U(1) gauge-field fluctuations. Performing the RG analysis in the one-loop level based on the dimensional regularization method, we reveal that such extremely overdamped dynamics of U(1) gauge-field fluctuations, which originates from the emergent one-dimensional dynamics of spinons, does not cause any renormalization effects to the effective dynamics of both critical charge fluctuations and spinon excitations. However, it turns out that the coupling between U(1) gauge-field fluctuations and both matter-field excitations still persists at this Mott transition, which results in novel mean-field dynamics to explain the nature of the spin-liquid Mott quantum criticality. We discuss physical implications of effective one-dimensional spin dynamics and extremely overdamped gauge dynamics at the Mott quantum criticality.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Plasmon coupling in topological insulator multilayers

Topological insulators (TIs) house two-dimensional Dirac plasmons on their surfaces. In TI thin films, plasmons on the top and bottom surfaces couple electrostatically, giving rise to an acoustic and an optical plasmon mode. By extension, a superlattice comprising TI layers and trivially-insulating layers could house multiple complex plasmon modes which could be used to create a new type of Dirac metamaterial. In this paper, we synthesize TI superlattices, fabricate them into stripe arrays, characterize their optical and plasmonic properties, and model the samples using transfer matrices. Furthermore, we excite plasmon modes that couple to the phonons in the superlattice, resulting in hybrid plasmon phonon polaritons. These modes are modeled using an analytical Fano resonance model and the extracted resonant positions are reproduced by transfer matrix modeling. We also excite an epsilon-near-zero mode in the top dielectric material (Bi 0.5 In 0.5 ) 2 Se 3 . Understanding the behavior of the polariton modes in this complex system will lend insight into the many-body interaction in low-dimensional systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Distinct Surface and Bulk Thermal Behaviors of LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode Materials as a Function of State of Charge

Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior ofLiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors or oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Proton-Coupled Electron Transfer Mechanisms for CO 2 Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine

Immobilized cobalt phthalocyanine (CoPc) is a highly promising architecture for the six-proton, six-electron reduction of CO 2 to methanol. This electroreduction process relies on proton-coupled electron transfer (PCET) reactions that can occur by sequential or concerted mechanisms. Immobilization on a conductive support such as carbon nanotubes or graphitic flakes can fundamentally alter the PCET mechanisms. We use density functional theory (DFT) calculations of CoPc adsorbed on an explicit graphitic surface model to investigate intermediates in the electroreduction of CO 2 to methanol. Our calculations show that the alignment of the CoPc and graphitic electronic states influences the reductive chemistry. These calculations also distinguish between charging the graphitic surface and reducing the CoPc and adsorbed intermediates as electrons are added to the system. This analysis allows us to identify the chemical transformations that are likely to be concerted PCET, defined for these systems as the mechanism in which protonation of a CO 2 reduction intermediate is accompanied by electron abstraction from the graphitic surface to the adsorbate without thermodynamically stable intermediates. Furthermore, this work establishes a mechanistic pathway for methanol production that is consistent with experimental observations and provides fundamental insight into how immobilization of the CoPc impacts its CO 2 reduction chemistry.

Adsorption↗
DOE OSTI2020

Reprint of "Selective conversion of CO into ethanol on Cu(511) surface reconstructed from Cu(pc): Operando studies by electrochemical scanning tunneling microscopy, mass spectrometry, quartz crystal nanobalance, and infrared spectroscopy"

A polycrystalline copper, surface-terminated by a well-defined (511)-oriented facet, was electrochemically generated by a series of step-wise surface reconstruction and iterations of mild oxidative-reductive processes in 0.1 M KOH. The electrochemical reduction of CO on the resultant stepped surface was investigated by four surface-sensitive operando methodologies: electrochemical scanning tunneling microscopy (STM), electrochemical quartz crystal nanobalance (EQCN), differential electrochemical mass spectrometry (DEMS), and polarization-modulation infrared spectroscopy (PMIRS). The stepped surface catalyzed the facile conversion of CO into ethanol, the exclusive alcohol product at a low overpotential of -1.06 V (SHE) or - 0.3 V (RHE). Additionally, the chemisorption of CO was found to be a necessary prelude to ethanol production; i.e. the surface coverages, rather than solution concentrations, of CO and its surface-bound intermediates primarily dictate the reaction rates (current densities). Contrary to the expected predominance of undercoordinated step-site reactivity over the coordination chemistry of vicinal surfaces, vibrational spectroscopic evidence reveals the involvement of terrace-bound CO adsorbates during the multi-atomic transformations associated with the production of ethanol.

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

Efficient Electrochemical Reduction of CO 2 to Formate in Methanol Solutions by Mn‐Functionalized Electrodes in the Presence of Amines**

Carbon cloth electrode modified by covalently attaching a manganese organometallic catalyst is used as cathode for the electrochemical reduction of CO 2 in methanol solutions. Six different industrial amines are employed as co-catalyst in millimolar concentrations to deliver a series of new reactive system. While such absorbents were so far believed to provide a CO 2 reservoir and act as sacrificial proton source, we herein demonstrate that this role can be played by methanol, and that the adduct formed between CO 2 and the amine can act as an effector or inhibitor toward the catalyst, thereby enhancing or reducing the production of formate. Pentamethyldiethylentriamine (PMDETA), identified as the best effector in our series, converts CO 2 in wet methanolic solution into bisammonium bicarbonate. Computational studies revealed that this adduct is responsible for a barrierless transformation of CO 2 to formate by the reduced form of the Mn catalyst covalently bonded to the electrode surface. As a consequence, selectivity can be switched on demand from CO to formate anion, and in the case of (PMDETA) an impressive TON HCOO- of 2.8×10 4 can be reached. This new valuable knowledge on an integrated capture and utilization system paves the way toward more efficient transformation of CO 2 into liquid fuel.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Elastomeric nematic colloids, colloidal crystals and microstructures with complex topology

Control of physical behaviors of nematic colloids and colloidal crystals has been demonstrated by tuning particle shape, topology, chirality and surface charging. However, the capability of altering physical behaviors of such soft matter systems by changing particle shape and the ensuing responses to external stimuli has remained elusive. We fabricated genus-one nematic elastomeric colloidal ring-shaped particles and various microstructures using two-photon photopolymerization. Nematic ordering within both the nano-printed particle and the surrounding medium leads to anisotropic responses and actuation when heated. With the thermal control, elastomeric microstructures are capable of changing from genus-one to genus-zero surface topology. Using these particles as building blocks, we investigated elastomeric colloidal crystals immersed within a liquid crystal fluid, which exhibit crystallographic symmetry transformations. Furthermore, our findings may lead to colloidal crystals responsive to a large variety of external stimuli, including electric fields and light. Pre-designed response of elastomeric nematic colloids, including changes of colloidal surface topology and lattice symmetry, are of interest for both fundamental research and applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enabling complete multichannel nonadiabatic dynamics: A global representation of the two-channel coupled, 1,2 1 A and 1 3 A states of NH 3 using neural networks

Global coupled three-state two-channel potential energy and property/interaction (dipole and spin–orbit coupling) surfaces for the dissociation of NH 3 (Ã) into NH + H 2 and NH 2 + H are reported. The permutational invariant polynomial-neural network approach is used to simultaneously fit and diabatize the electronic Hamiltonian by fitting the energies, energy gradients, and derivative couplings of the two coupled lowest-lying singlet states as well as fitting the energy and energy gradients of the lowest-lying triplet state. The key issue in fitting property matrix elements in the diabatic basis is that the diabatic surfaces must be smooth, that is, the diabatization must remove spikes in the original adiabatic property surfaces attributable to the switch of electronic wavefunctions at the conical intersection seam. Here, we employ the fit potential energy matrix to transform properties in the adiabatic representation to a quasi-diabatic representation and remove the discontinuity near the conical intersection seam. The property matrix elements can then be fit with smooth neural network functions. The coupled potential energy surfaces along with the dipole and spin–orbit coupling surfaces will enable more accurate and complete treatment of optical transitions, as well as nonadiabatic internal conversion and intersystem crossing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Application of electron backscatter diffraction techniques to quantify effects of aging on sub-grain and spatial heterogeneity in NMC cathodes

Identification and evaluation of structural heterogeneity in spent cathode materials is crucial to developing appropriate remediation strategies for novel recycling processes. Native heterogeneities may be exacerbated during the cell's operational lifetime, as sub-particle-scale variations induce anisotropic expansion and contraction upon cycling. Structural transformations resulting from repeated cycling and calendar aging predominantly occur at the secondary particle surface and at the grain boundaries (GBs) between primary particles. However, the diffusion and stress build up around and across GBs are poorly understood. In this study, electron backscatter diffraction (EBSD) is employed to track sub-grain lattice structure across a statistically relevant number of Li(Ni0.33Mn0.33Co0.33)O2 (NMC-111) particles. Specifically, differences in lattice misorientation – measured as the deviation from the grain's average orientation – are tracked as a function of position within the electrode (near current collector, middle, and near separator) and as a function of electrochemical cycling. Further, a novel method of structural analysis is developed, offering insight into sub-grain diffusion behavior by comparing lattice misorientation near the grain boundary versus in the grain bulk. The present results suggest that electrode-scale spatial heterogeneity in lattice structure is induced by initial manufacturing conditions, and that radial gradients in lattice misorientation evolve at the primary particle scale with repeated electrochemical cycling.

25 ENERGY STORAGE↗
DOE OSTI2026

Reducing Non-Radiative Recombination in Perovskite Solar Cells with a SiO2-Graphene Oxide Buried Interface Layer

Perovskite solar cells (PSCs) have emerged as a transformative photovoltaic technology. However, the device performance of inverted PSCs is dramatically limited by surface defects and the underlying film morphology of metal halide perovskite (MHP) thin film. Herein, we report a novel buried interface layer consisting of SiO2 nanoparticles (NPs) chemically bonded to graphene oxide (GO), deposited atop a hydrophobic hole extraction layer (HEL) to address this limitation. The SiO2 NPs serve as insoluble scaffolds that immobilize GO sheets on the hydrophobic HEL surface, enabling the formation of homogeneous MHP thin films. Meanwhile, the GO functional groups interact with surface-uncoordinated Pb2+, suppressing interfacial defects and guiding crystal grain growth of the resultant MHP thin films. This synergistic effect suppresses non-radiative charge recombination and enhances charge extraction efficiency. As a result, a 26.07% efficiency with significantly suppressed photocurrent hysteresis is observed from PSCs incorporating the SiO2-GO buried interface layer. Moreover, the above PSCs maintain 92% of their initial PCE after 1800 h of continuous operation at the maximum power point under AM 1.5 G (100 mW/cm2) illumination at 25 degrees C in air with 50-60% relative humidity. These results demonstrate that we have developed a facile and effective way to realize high-performance inverted PSCs.

14 SOLAR ENERGY↗
DOE OSTI2023

Automated Reaction Kinetics of Gas-Phase Organic Species over Multiwell Potential Energy Surfaces

Automation of rate-coefficient calculations for gas-phase organic species became possible in recent years and has transformed how we explore these complicated systems computationally. Kinetics workflow tools bring rigor and speed and eliminate a large fraction of manual labor and related error sources. In this paper we give an overview of this quickly evolving field and illustrate, through five detailed examples, the capabilities of our own automated tool, KinBot. Here we bring examples from combustion and atmospheric chemistry of C-, H-, O-, and N-atom-containing species that are relevant to molecular weight growth and autoxidation processes. The examples shed light on the capabilities of automation and also highlight particular challenges associated with the various chemical systems that need to be addressed in future work.

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

Modulating Surface Anionic Redox Chemistry toward Highly Stable Li-Rich Cathodes with Negligible Oxygen Loss

Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). Here, in this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO 3 2- /SO 4 2- redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Plasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NO x

Supported nanoclusters (SNCs) with distinct geometric and electronic structures have garnered significant attention in the field of heterogeneous catalysis. However, their directed synthesis remains a challenge due to limited efficient approaches. This study presents a plasma-assisted treatment strategy to achieve supported metal oxide nanoclusters from a rapid transformation of monomeric dispersed metal oxides. As a case study, oligomeric vanadia-dominated surface sites were derived from the classic supported V 2 O 5 -WO 3 /TiO 2 (VWT) catalyst and showed nearly an order of magnitude increase in turnover frequency (TOF) value via an H 2 -plasma treatment for selective catalytic reduction of NO with NH 3 . Such oligomeric surface VO x sites were not only successfully observed and firstly distinguished from WO x and TiO 2 by advanced electron microscopy, but also facilitated the generation of surface amide and nitrates intermediates that enable barrier-less steps in the SCR reaction as observed by modulation excitation spectroscopy technologies and predicted DFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗