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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Revolutionizing Methane Transformation with the Dual Production of Aromatics and Electricity in a Protonic Ceramic Electrocatalytic Membrane Reactor

Reducing the energy and carbon intensity of the conventional chemical processing industry can be achieved by electrochemically transforming natural gases into higher-value chemicals with higher efficiency and near-zero emissions. In this work, the direct conversion of methane to aromatics and electricity has been achieved in a protonic ceramic electrocatalytic membrane reactor through the integration of a proton-conducting membrane assembly and a trimetallic Pt–Cu/Mo/ZSM-5 catalyst for the nonoxidative methane dehydro-aromatization reaction. In this integrated system, a remarkable 15.6% single-pass methane conversion with an 11.4% benzene yield has been demonstrated, while a peak power density of 276 mW cm –2 is obtained at 700 °C. The enhanced 15.7% increase in conversion and 16.0% improvement in the yield are observed when compared with the thermochemical process, which is attributed to the shift of reaction equilibrium by the removal of hydrogen through the protonic membrane. Concurrently, the faster H2 removal at a higher electrical current gave rise to a higher methane conversion and benzene yield. Furthermore, the catalyst can be efficiently regenerated by eliminating carbon deposition. A stable cell potential is maintained for 45 h under a constant current load of 0.13 A cm –2 . Lastly, the dual production of aromatics and electricity in the electrocatalytic membrane reactor has been demonstrated to be an attractive approach for decarbonizing chemical processing.

aromatic compounds↗
DOE OSTI2021

Spatio-temporal ablation dynamics and plasma chemistry of aluminum induced by temporally modulated ytterbium fiber laser

Here, in this work, we studied single-pulse ablation dynamics of a temporally modulated continuous wave laser-material interaction with Al using in situ multimodal time-resolved diagnostics that describe in detail the associated physical and chemical processes. Time-resolved scattering, emission imaging, and optical emission spectroscopy unveiled a sequence of events spread out across three distinct phases: (i) early phase ablation process, associated with particle generation and liquid Al column formation (<20 μs), (ii) secondary detonation when sufficient ejected material is accumulated over the surface (20-50 μs), and (iii) molten liquid Al pool oscillation on the surface, followed by large droplet ejection from the liquid pool (100-500 μs). Atomic Al and AlO were observed with optical emission spectroscopy at different ratios during the entire lifetime of the event, verifying the formation of oxidized Al vapor upon its interaction with air. Morphological and compositional characterization confirmed surface oxidation and material re-solidification in the form of protrusions produced during the irradiation process. This work provides insights into the complex physical and chemical mechanisms of single-pulse ablation in the sub-millisecond laser pulse regime, which are critically important for parameter optimization in a variety of laser processing, microfabrication, and deposition applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Capturing Coupled Structural and Electronic Motions During Excited-State Intramolecular Proton Transfer via Computational Multiedge Resonant Inelastic X-ray Scattering

Proton-transfer processes build the foundation of many chemical processes. In Excited State Intramolecular Proton Transfer (ESIPT) processes the proton transfer process is impulsively started through light. Here, in this study, we explore the changes in coupled atomic and electronic motions during and following ESIPT through computational time-resolved Resonant Inelastic X-ray Scattering (trRIXS). Excited-state Ab Initio Molecular Dynamics (AIMD) simulations combined with Time-Dependent Density Functional Theory (TDDFT) calculations were performed for 10-hydroxybenzo[h]quinoline to obtain trRIXS signatures. RIXS at both the nitrogen and oxygen K-edges were computed to resolve the dynamics electronic structure from both the proton donor and acceptor perspective. The results show how RIXS can reveal the local electronic structure, the coupling between different electronic states and how electronic structure and coupling change during the proton transfer process. Additionally, we observe a strong correlation between spectral changes and structural changes during ESIPT.

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

Inertial dynamics of an interface with interfacial mass flux: Stability and flow fields’ structure, inertial stabilization mechanism, degeneracy of Landau’s solution, effect of energy fluctuations, and chemistry-induced instabilities

This work focuses on the long-standing problem of inertial dynamics of an interface with interfacial mass flux and reports new mechanisms for the interface stabilization and destabilization. The interface is a phase boundary separating fluids of different densities and having interfacial mass flux. To analyze the interface dynamics from a far field, we develop and apply the general matrix method to rigorously solve the boundary value problem involving the governing equations in the fluid bulk and the boundary conditions at the interface and at the outside boundaries of the domain. We find the fundamental solutions for the linearized system of equations and analyze the interplay of interface stability with flow fields’ structure by directly linking rigorous mathematical attributes to physical observables. We find that the interface is stable when the dynamics conserves the fluxes of mass, momentum, and energy; the stabilization is due to an inertial mechanism causing small oscillations of the interface velocity. In the classic Landau’s dynamics, the postulate of perfect constancy of the interface velocity leads to the development of Landau–Darrieus instability. This destabilization is also linked to the imbalance of the perturbed energy at the interface. The classic Landau’s solution is found to have degeneracy; lifting of the degeneracy may lead to singularity and self-similar dynamics. Our results compare well with traditional theories of combustion and propose new experiments to study the dynamics of the interface and the flow fields in combustible systems. We further conduct reactive molecular dynamics simulations to elucidate the complexity of chemical processes, to study the destabilizing effect of energy fluctuations on the interface stability, and to illustrate the chemistry-induced instabilities. In summary, we identify the extreme sensitivity of the interface dynamics to the interfacial boundary conditions, including the formal properties of fundamental solutions and the qualitative and quantitative properties of the flow fields. This provides new opportunities for studies, diagnostics, and control of multiphase flows in a broad range of processes in nature and technology.

42 ENGINEERING↗
DOE OSTI2021

Metabolic engineering of non-pathogenic microorganisms for 2,3-butanediol production

2,3-Butanediol (2,3-BDO) is a promising commodity chemical with various industrial applications. While petroleum-based chemical processes currently dominate the industrial production of 2,3-BDO, fermentation-based production of 2,3-BDO pro- vides an attractive alternative to chemical-based processes with regards to economic and environmental sustainability. The achievement of high 2,3-BDO titer, yield, and productivity in microbial fermentation is a prerequisite for the production of 2,3-BDO at large scales. Also, enantiopure production of 2,3-BDO production is desirable because 2,3-BDO stereoisomers have unique physicochemical properties. Pursuant to these goals, many metabolic engineering strategies to improve 2,3-BDO pro- duction from inexpensive sugars by Klebsiella oxytoca, Bacillus species, and Saccharomyces cerevisiae have been developed. Furthermore, this review summarizes the recent advances in metabolic engineering of non-pathogenic microorganisms to enable efficient and enantiopure production of 2,3-BDO.

2,3-BDO stereoisomers↗
DOE OSTI2022

Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics

Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, in this paper, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au 20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au 20 beyond the Born–Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au 20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7 ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au 20 cluster. Furthermore, our simulations show that the lifetime of the phonon-induced plasmon dephasing process is ~10.4 fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.

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

Advances in Carbon Capture and Use (CCU) Technologies: A Comprehensive Review and CO2 Mitigation Potential Analysis

One of society’s major current challenges is carbon dioxide emissions and their consequences. In this context, new technologies for carbon dioxide (CO2) capture have attracted much attention. One of these is carbon capture and utilization (CCU). This work focuses on the latest trends in a holistic approach to carbon dioxide capture and utilization. Absorption, adsorption, membranes, and chemical looping are considered for CO2 capture. Each CO2 capture technology is described, and its benefits and drawbacks are discussed. For the use of carbon dioxide, various possible applications of CCU are described, starting with the utilization of carbon dioxide in agriculture and proceeding to the conversion of CO2 into fuels (catalytic processes), chemicals (photocatalytic processes), polymers, and building supplies. For decades, carbon dioxide has been used in industrial processes, such as CO2-enhanced oil recovery, the food industry, organic compound production (such as urea), water treatment, and, therefore, the production of flame retardants and coolants. There also are several new CO2-utilization technologies at various stages of development and exploitation, such as electrochemical conversion to fuels, CO2-enhanced oil recovery, and supercritical CO2. At the end of this review, future opportunities are discussed regarding machine learning (ML) and life cycle assessment (LCA).

Peres, Christiano B.↗
DOE OSTI2022

Triacetic Acid Lactone and 4-Hydroxycoumarin as Bioprivileged Molecules for the Development of Performance-Advantaged Organic Corrosion Inhibitors

Biomass conversion, especially the development of bioprivileged molecules utilizing integration of biological and chemical processes, has shown potential to produce novel chemicals with enhanced properties. Here, organic corrosion inhibitors based on triacetic acid lactone and 4-hydroxycoumarin have been synthesized in good yield and tested for corrosion inhibition on mild steel in both sulfuric acid and hydrochloric acid. Sixteen novel corrosion inhibitors derived from triacetic acid lactone and 4-hydroxycoumarin were efficiently synthesized and twelve of them showed high corrosion inhibition efficiency as confirmed by electrochemical impedance spectroscopy (giving values greater than 78%) and polarization analysis. While triacetic acid lactone-based compounds showed good corrosion inhibition performance, the 4-hydroxycoumarin-based compounds showed further improvement in corrosion inhibition performance. Scanning electron microscopy (SEM) analysis of the mild steel coupon in the presence of selected inhibitors showed that corrosion was significantly diminished, with complementary X-ray photoelectron spectroscopy (XPS) analysis suggesting the inhibitor molecules strongly adsorbed on the steel surface. Quantum chemical calculations showed poor correlation between calculated parameters and the performance of these molecules. This large set of corrosion inhibitors containing a dozen promising corrosion inhibitors is useful for future rational design of corrosion inhibitors. In conclusion, the results demonstrate a new direction for the development of bioprivileged molecules.

09 BIOMASS FUELS↗
DOE OSTI2020

Noncontact Flow Rate Using Laser Ultrasonics

Several types of advanced nuclear reactors are cooled with high-temperature liquid metal or molten salt flows. There is a critical need to measure flow velocity in flow channels for test purposes, and eventually in operational reactors. In conventional ultrasonic flow sensors, ultrasonic waves traveling in both the upstream and downstream directions are generated and detected by transducers that must contact the flow channels. A shift in the frequency or transit time between the two ultrasonic waves is measured to determine flow velocity. We describe here an initial effort to apply that sensing concept when the contact transducers are replaced by laser-based generation and detection instrumentation. This noncontact sensing avoids many practical problems associated with contact transducers when implemented on flow channels at high temperature. Laser-based flow monitoring can also be applied to hot-process piping in the geothermal energy, chemical-processing and petroleum-refining industries. Our effort has included theoretical simulation of noncontact laser-based flow monitoring, indicating capability of measuring flow velocities relevant to reactor cooling. It also included a room-temperature experimental demonstration using water as the flow liquid, and indicating capability of measuring flow velocity at a responsivity roughly consistent with simulation predictions. Plans were made for an experimental demonstration at Oregon State University using liquid metal at 110 degrees C.

02 PETROLEUM↗
DOE OSTI2021

Progress Towards a New Model Chemolithoautotrophic Host (CRADA Final Report)

Some of the largest scale chemical processes for the production of important commodity chemicals and fuels involve an H 2 -containing gas mixture as an intermediate [e.g. ammonia, urea, methanol, Fischer-Tropsch (F-T) diesel, and hydrotreatment of crude petroleum to refined fuels]. The successful development of a model H 2 -oxidizing chemoautotrophic host could expand the range of fuels and chemicals produced from H 2 and CO 2 intermediates in the chemical, oil, and gas sectors in the near term, as well as from renewable and waste-derived sources of these gases that are expected to greatly expand in coming years. Among non-photosynthetic bacteria that can utilize H 2 and CO 2 , Cupriavidus necator (C. necator, formerly Ralstonia eutropha), is the best studied. C. necator is an excellent microbial host for the production of a variety of chemicals because it grows extremely quickly to very high cell densities autotrophically on H 2 and CO 2 , is genetically tractable, and has the ability to accumulate polymers, such as polyhydroxybutyrate, at industrial levels. Despite having great potential as a platform bioproduction host, genetic tools are limited, making metabolic engineering of this organism slow and laborious. In this CRADA project, we developed a number of genetic tools for C. necator: 1) Improvement of C. necator genetic transformation efficiency 2) Integration of heterologous genes into the C. necator chromosome and development of promoter library 3) Development of graded RBSs to control heterologous protein expression 4) Use of RBSs to demonstrate fatty alcohol production in C. necator 5) Demonstration of CRISPR-Cas9 gene editing in C. necator

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

Constrained nuclear–electronic orbital method for periodic density functional theory: Application to H 2 chemisorption on Si(001) surfaces

The nuclear–electronic orbital (NEO) method provides a powerful computational framework for incorporating nuclear quantum effects (NQE) in electronic structure calculations beyond the Born–Oppenheimer approximation. By incorporating additional constraints to the position operator on quantum particles like protons, the NEO method enables calculation of effective potential that accounts for NQE. Here, in this work, we present a new constrained NEO (cNEO) formulation for density functional theory (cNEO-DFT) calculations in the context of extended periodic systems. Using the nudged elastic band method, we discuss an application of the cNEO-DFT approach to studying the adsorption of a hydrogen molecule on the Si(001) surfaces. The calculation shows how NQE impacts the reaction energetics. The proton density changes are computed along the reaction pathways. This work demonstrates the capability of the new cNEO-DFT method to study a wide range of chemical processes, such as surface reactions where the quantum nature of light atoms like protons is non-negligible.

Chemical processes↗
DOE OSTI2024

Reactor wall effects in Si–Cl 2 –Ar atomic layer etching

This work complements our previous manuscript [J. Vac. Sci. Technol. A41, 062602 (2023)] where predictions from molecular dynamics (MD) simulations of silicon–chlorine–argon (Si–Cl 2 –Ar) atomic layer etching (ALE) are compared to experiments. When etch product distributions for atomic chlorine (Cl) and silicon chlorides were initially compared to optical emission spectroscopy (OES) signals, it appeared that there was a discrepancy between the MD predictions and experimental results at higher ion fluences. Experiments showed a relatively long period of nearly constant Cl-containing etch products released from the ion-bombarded surface (referred to as the “plateau”) but this effect was not observed in MD simulations. In this report, we demonstrate that the “plateau” observed in the OES signals is most likely due to the desorption of Cl-containing etch products from the walls of the reactor and subsequent adsorption on the Si substrate. Experiments varying the gas residence time in the chamber while keeping incoming gas concentrations and pressure constant support this interpretation. We also conducted experiments with an additional Ar-only flow in the chamber to reduce the concentration of Cl-containing species on the chamber walls. For both sets of flow modification experiments, we observe results consistent with the hypothesis that Cl-containing species desorbing from chamber walls are a significant cause of the observed discrepancy between MD predictions and experimental observations. If the measured OES signals are corrected for this “additional” source of Cl-containing species at the surface, the MD predictions and measured OES signals are in excellent agreement. This further supports the predictive capability of MD simulations to accurately capture the relevant physical and chemical processes in plasma-assisted ALE processes. We provide an order of magnitude estimate of the required density of Cl-containing species that would account for the additional etch products observed. Finally, we discuss the implications of this effect on ALE in plasma nanofabrication.

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

Autothermal Chemical Looping Oxidative Dehydrogenation of Ethane: Redox Catalyst Performance, Longevity, and Process Analysis

Energy-efficient upgrading of stranded ethane from shale gas to olefins holds the promise of increasing the supply of useful chemical feedstocks while reducing flaring-based CO 2 emissions. Previously, we reported a modular ethane-to-liquids (M-ETL) system based on a chemical looping oxidative dehydrogenation (CL-ODH) scheme. In this article, we present long-term (>1200 h) results of Li 2 CO 3 -promoted La 0.8 Sr 0.2 FeO 3 corresponding to ~4125 CL-ODH cycles in a large laboratory-scale packed bed reactor. Temperature monitoring along the bed length confirmed the exothermicity of both the oxidative dehydrogenation and regeneration steps, enabling an autothermal operation. Product gas analysis indicated that the redox catalyst maintains a high C 2+ selectivity (~90%) and ethane conversion (~67%) at 735 °C after continuous cycling of >1000 h. As a result, product distributions and heats of reactions were used to update our M-ETL process model for revised techno-economic analysis, demonstrating that the current system is economically viable with relatively low required selling prices across a wide range of operating scenarios.

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

Single-Molecule Chemical Reactions Unveiled in Molecular Junctions

Understanding chemical processes at the single-molecule scale represents the ultimate limit of analytical chemistry. Single-molecule detection techniques allow one to reveal the detailed dynamics and kinetics of a chemical reaction with unprecedented accuracy. It has also enabled the discoveries of new reaction pathways or intermediates/transition states that are inaccessible in conventional ensemble experiments, which is critical to elucidating their intrinsic mechanisms. Thanks to the rapid development of single-molecule junction (SMJ) techniques, detecting chemical reactions via monitoring the electrical current through single molecules has received an increasing amount of attention and has witnessed tremendous advances in recent years. Research efforts in this direction have opened a new route for probing chemical and physical processes with single-molecule precision. This review presents detailed advancements in probing single-molecule chemical reactions using SMJ techniques. We specifically highlight recent progress in investigating electric-field-driven reactions, reaction dynamics and kinetics, host–guest interactions, and redox reactions of different molecular systems. Finally, we discuss the potential of single-molecule detection using SMJs across various future applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal–Organic Framework Material

Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO 4 N] node controlled by the specific host–guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. In this work, we have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H 2 O upon dehydration to give MFM-520. Filling MFM-520 with CO 2 and SO 2 reveals that, while CO 2 has a minimal structural influence, SO 2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO 2 under flue-gas desulfurization conditions, and the facile release of captured SO 2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO 2 .

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

Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries

To understand the origins of failure and limited cycle life in lithium-ion batteries (LIBs), it is imperative to quantitatively link capacity-fading mechanisms to electrochemical and chemical processes. This is extremely challenging in real systems where capacity is lost during each cycle to both active material loss and solid electrolyte interphase (SEI) evolution, two indistinguishable contributions in traditional electrochemical measurements. Here, we have used a model system in combination with (1) precision measurements of the overall Coulombic efficiency via electrochemical experiments and (2) x-ray reflectivity measurements of the active material losses. The model system consisted of a 515 Å thick amorphous silicon (a-Si) thin film on silicon carbide in half-cell geometry using a carbonate electrolyte with LiPF6 salt. This approach allowed us to quantify the capacity lost during each cycle due to SEI evolution. Combined with electrochemical analysis, we identify SEI growth as the major contribution to capacity fading. Specifically, the continued SEI growth results in increasing overpotentials due to increased SEI resistance, and this leads to lower extent of lithiation when the cutoff voltage is reached during lithiation. Our results suggest that SEI grows more with increased time spent at low voltages where electrolyte decomposition is favored. Finally, we extracted a proportionality constant for SEI growth following a parabolic growth law. Our methodology allows for the quantitative determination of lithium-ion loss mechanisms in LIBs by separately tracking lithium ions within the active materials and the SEI and offers a powerful method of quantitatively understanding LIB loss mechanisms.

25 ENERGY STORAGE↗