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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 1,513 records · Page 84
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Role of Quinones in Electron Transfer of PQQ–Glucose Dehydrogenase Anodes—Mediation or Orientation Effect

In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-dependent glucose dehydrogenase (PQQ–sGDH) anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2025

Combining Theory and Experiment to Map the Atomic-Level Structure–Energy Pathways of Adsorbate-Mediated Phase Changes in a Cooperatively Flexible Metal–Organic Framework

An important subclass of metal–organic frameworks (MOFs) exhibits cooperative flexibility, wherein individual crystallites undergo global structural phase changes in response to external stimuli. Where cooperative flexibility results in reversible changes between crystalline states of distinct accessible porosity, these frameworks can exhibit rare yet desirable behaviors that cannot be explained by local dynamics alone. Yet, the chemical and structural origins of cooperative flexibility and how frameworks undergo these reversible phase changes at the atomic level remain poorly understood. Deliberate design for specific applications is therefore exceedingly difficult, and there is great impetus to develop a fundamental understanding of this phenomenon. Here, an effective and widely accessible computational approach is developed, which is designed to provide microscopic resolution via direct comparison to experimental data along the desorption-guided pathway. The strategy is applied to explain the desorption-induced phase change in an experimentally well-characterized framework, CdIF-13 (sod-Cd(benzimidazolate)2), where experiment alone was unable to resolve the atomistically detailed phase change landscape. Our findings reveal that the cooperative phase change pathways are adsorbate dependent with thermodynamics of intermediate structural states dictated by a nuanced interplay of ligand orientation, skeletal symmetry, and modes of surface adsorption. The results reveal that this isotropically flexible framework is “chaperoned” through a complex energy landscape by specific adsorbates, revealed by the reported computational approach with atomic-level insight and validated by experimentally determined structures. Thus, this work facilitates both understanding and future design of flexible materials for applications in gas storage, transport, delivery, and separation technologies.

03 NATURAL GAS↗
DOE OSTI2025

Unveiling the Origin of Morphological Instability in Topologically Complex Electrocatalytic Nanostructures

Coarsening and degradation phenomena in metals have largely focused on thermally driven processes, such as bulk and surface diffusion. However, dramatic coarsening has been reported in high-surface-area, nanometer-sized Pt-based catalysts during potential cycling in an electrolyte at room temperature─a temperature too low for the process to be explained purely by surface mobility values measured in both vacuum and electrolytes (∼10 –22 and ∼10 –18 cm 2 /s, respectively). This morphological evolution must be due to a different mechanism for mass transport that is sensitive to electrochemical conditions (e.g., electrolyte composition, potential limits, and scan rate). However, there have been no notable studies of electrochemically induced coarsening in nanometer-sized electrocatalysts. Here, we unveil the origins of coarsening in an electrolyte through coupled in situ experiments and atomistic kinetic Monte Carlo (kMC) simulations. Our work demonstrates electrochemical coarsening is driven by two concurrent mechanisms that can be explained at the atomistic level: (i) dissolution/redeposition during the reduction of an oxidized species and (ii) rapid surface diffusion of undercoordinated atoms.

gold↗
DOE OSTI2025

Understanding the Competition between Alcohol Formation and Dimerization during Electrochemical Reduction of Aromatic Carbonyl Compounds

The electrochemical reductive dimerization of small aromatic carbonyl compounds derived from lignocellulosic biomass is a crucial C−C coupling reaction for upgrading small molecules to longchain hydrocarbons, particularly in the synthesis of drop-in sustainable aviation fuels. Although other electrochemical reduction reactions of these reactants (i.e., hydrogenation and hydrogenolysis) have undergone extensive mechanistic investigation, the understanding of dimerization remains relatively underdeveloped. Most importantly, there is a lack of understanding of the selectivity-determining step between dimerization and monomer reduction and critical factors that can affect this step. In this study, we provide a comprehensive mechanistic model to explain the competition between dimerization and monomer reduction of benzaldehyde under various conditions. Our model proposes that the selectivity between dimerization and monomer reduction depends on the competition between desorption of a ketyl radical from the electrode, necessary for dimerization, and further reduction of the ketyl radical to an alcohol on the electrode by proton-coupled electron transfer (PCET). Computationally comparing the adsorption/desorption energy and PCET activation barrier energy is challenging because conventional DFT calculations substantially underestimate the PCET kinetic barriers. In this study, we employed constrained DFTbased configuration interaction (CDFT-CI) to obtain a reliable comparison of these energies. Our mechanistic model was tested and supported by experimental results obtained with four electrodes (Cu, Pb, Bi, graphite), three pH conditions (acidic, neutral, basic), and three potentials. Our study offers a coherent mechanistic foundation that can explain how each of these conditions impacts the desorption and PCET processes and the selectivities for dimerization and alcohol production.

09 BIOMASS FUELS↗
DOE OSTI2018

Origin of Broad Emission Spectra in InP Quantum Dots: Contributions from Structural and Electronic Disorder

The ensemble emission spectra of colloidal InP quantum dots are broader than achievable spectra of cadmium- and lead-based quantum dots, despite similar single-particle line widths and significant efforts invested in the improvement of synthetic protocols. Here, we seek to explain the origin of persistently broad ensemble emission spectra of colloidal InP quantum dots by investigating the nature of the electronic states responsible for luminescence. We identify a correlation between red-shifted emission spectra and anomalous broadening of the excitation spectra of luminescent InP colloids, suggesting a trap-associated emission pathway in highly emissive core shell quantum dots. Time-resolved pump probe experiments find that s are largely untrapped on photoluminescence relevant time scales pointing to emission from recombination of localized holes with free electrons. Two-dimensional electronic spectroscopy on InP quantum dots reveals multiple emissive states and increased electron phonon coupling associated with hole localization. These localized hole states near the valence band edge are hypothesized to arise from incomplete surface passivation and structural disorder associated with lattice defects. We confirm the presence and effect of lattice disorder by X-ray absorption spectroscopy and Raman scattering measurements. Participation of localized electronic states that are associated with various classes of lattice defects gives rise to phonon-coupled defect related emission. These findings explain the origins of the persistently broad emission spectra of colloidal InP quantum dots and suggest future strategies to narrow ensemble emission lines comparable to what is observed for cadmium-based materials.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Theoretical Study of C-H Bond Cleavage via Concerted Proton-Coupled Electron Transfer in Fluorenyl-Benzoates

Developing new strategies to activate and cleave C-H bonds is important for a broad range of applications. Recently a new approach for C-H bond activation using multi-site concerted proton-coupled electron transfer (PCET) involving intermolecular electron transfer to an oxidant coupled to intramolecular proton transfer was reported. For a series of oxidants reacting with 2-(9H-fluoren-9-yl)benzoate, experimental studies revealed an atypical Brønsted a, defined as the slope of the logarithm of the PCET rate constant versus the logarithm of the equilibrium constant or the scaled driving force. Herein this reaction is modeled with a vibronically nonadiabatic PCET theory. Hydrogen tunneling, thermal sampling of the proton donor-acceptor mode, solute and solvent reorganization, and contributions from excited vibronic states are found to play important roles. The calculations qualitatively reproduce the experimental observation of a Brønsted a significantly less than 0.5 and explain this shallow slope in terms of exoergic processes between pairs of electron-proton vibronic states. These fundamental mechanistic insights may guide the design of more effective strategies for C-H bond activation and cleavage.

Sayfutyarova, Elvira R.↗
DOE OSTI2019

Role of Solvation on Diffusion of Ions in Diblock Copolymers: Understanding the Molecular Weight Effect through Modeling

Salt-doped diblock copolymers with microphase-separated domains of both an ion conductive and a mechanically strong polymer have been extensively studied due to their potential in transport applications. Several unusual or counterintuitive trends regarding their transport properties have been observed experimentally, such as increasing ion conduction as a function of molecular weight. A vital feature of these systems is the strong solvation of ions in the conducting microphase due to its higher dielectric constant. Herein, we perform molecular dynamics simulations using a coarse-grained model that includes a 1/r 4 potential form to generically represent ion solvation, allowing us to reproduce experimentally observed trends and explore their molecular underpinnings. We find that increasing ion concentration can increase or decrease ion diffusion, depending on solvation strength. We further show that the trend of increasing diffusion with molecular weight becomes more dramatic as ions are solvated in one polymer block more strongly or as the ion-ion interactions get stronger. In contrast to expectations, the interfacial width or the overlap of ions with the nonconductive polymer block do not adequately explain this phenomenon; instead, local ion agglomeration best explains reduced diffusion. Interfacial sharpening, controlled by the Flory chi parameter and molecular weight, tends to allow ions to spread more uniformly, and this increases their diffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Origin of Abrupt Rise in Deuteron NMR Longitudinal Relaxation Times of Protein Methyl Groups Below 90 K

In order to examine the origin of the abrupt change in the temperature dependence of NMR longitudinal relaxation times observed earlier for methyl groups of L69 in the hydrophobic core of villin headpiece protein at around 90 K (Vugmeyster et al. J. Am. Chem. Soc. 2010, 132, 4038), we extended the measurements to several other methyl groups in the hydrophobic core. We show that for all methyl groups, relaxation times experience a dramatic jump several orders of magnitude around this temperature. Theoretical modeling supports the conclusion that the origin of the apparent transition in the relaxation times is due to the existence of the distribution of conformers distinguished by their activation energy for methyl three-site hops. It is also crucial to take into account the differential contribution of individual conformers into overall signal intensity. When a particular conformer approaches the regime at which its three-site hops rate constant is on the order of the quadrupolar coupling interaction constant, the intensity of the signal due to this conformer experiences a sharp drop, thus changing the balance of the contributions of different conformers into the overall signal. As a result, the observed apparent transition in the relaxation rates can be explained without the assumption of an underlying transition in the rate constants. This work in combination with earlier results also shows that the model based on the distribution of conformers explains the relaxation behavior in the entire temperature range between 300-70 K.

cryogenic temperature↗
DOE OSTI2015

Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene

Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4- methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO 3 - ) based ionization scheme. Also, the experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO 2 ) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. Our conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D 2 O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Adsorption and Reaction of Methanol over CeO X (100) Thin Films

Methanol was adsorbed on oxidized and reduced CeO X (100) thin films to probe the active sites and reaction selectivity of these surfaces compared to those of CeO X (111). Roughly twice as much methoxy was formed on oxidized CeO 2 (100) compared to that formed on CeO 2 (111). In addition to more methoxy, hydroxyl is also more stable on CeO 2 (100). Unlike on CeO 2 (111), however, methanol on CeO 2 (100) produced CO, CO 2 , and H 2 in addition to water and formaldehyde. The behavior of CeO 2 (100) is related to its surface structure, which provides greater access to Ce cations and therefore more active adsorption sites and more highly undercoordinated Ce and O. The undercoordinated O may explain the enhanced dehydrogenation activity leading to CO and H 2 formation. The reduction of ceria leads to increased methanol uptake on both CeO 2 – X (100) and CeO 2 – X (111). However, although the uptake doubled on reduced CeO 2 – X (111) compared to the oxidized surface, it increased by only 10% on reduced CeO 2 – X (100) compared to that on fully oxidized CeO 2 (100). Reduction of both surfaces leads to a greater production of CO and H 2 . Reaction on all surfaces progresses rapidly from methoxy to products. Lastly, there is no spectroscopic evidence of formyl or formate intermediates. On CeO X (100), carbonate is detected that decomposes into CO 2 at high temperature.

Albrecht, P↗
DOE OSTI2019

Exploring the Effect of Aspect to Inform Future Earthcasts of Climate-Driven Changes in Weathering of Shale

Projections of future conditions within the critical zone—earthcasts—can be used to understand the potential effects of changes in climate on processes affecting landscapes. We are developing an approach to earthcast how weathering will change in the future using scenarios of climate change. As a first step here, we use the earthcasting approach to model aspect-related effects on soil water chemistry and weathering on hillsides in a well-studied east-west trending watershed (Shale Hills, Pennsylvania, USA). We completed model simulations of solute chemistry in soil water with and without the effect of aspect for comparison to catchment observations. With aspect included, aqueous weathering fluxes were higher on the sunny side of the catchment. But the effect of aspect on temperature (0.8 °C warmer soil on sunny side) and recharge (100 mm/year larger on shaded side) alone did not explain the magnitude of the observed higher weathering fluxes on the sunny side. We note modeled aspect-related differences in weathering fluxes only approach field observations when we incorporated the measured differences in clay content observed in augered soils on the two hillslopes. We also had to include a biolifting module to accurately describe cation concentrations in soil water versus depth. Biolifting lowered some mineral dissolution rates while accelerating kaolinite precipitation. These short-duration simulations also highlighted that the inherited differences in particle size on the two sides of the catchment might in themselves be explained by weathering under different microclimates caused by aspect—over longer durations than simulated with our models.

58 GEOSCIENCES↗
DOE OSTI2019

Transport and Loss of Ring Current Electrons Inside Geosynchronous Orbit During the 17 March 2013 Storm

Ring current electrons (1–100 keV) have received significant attention in recent decades, but many questions regarding their major transport and loss mechanisms remain open. In this study, we use the four-dimensional Versatile Electron Radiation Belt code to model the enhancement of phase space density that occurred during the 17 March 2013 storm. Our model includes global convection, radial diffusion, and scattering into the Earth's atmosphere driven by whistler-mode hiss and chorus waves. We study the sensitivity of the model to the boundary conditions, global electric field, the electric field associated with subauroral polarization streams, electron loss rates, and radial diffusion coefficients. The results of the code are almost insensitive to the model parameters above 4.5 R E R E , which indicates that the general dynamics of the electrons between 4.5 R E and the geostationary orbit can be explained by global convection. We found that the major discrepancies between the model and data can stem from the inaccurate electric field model and uncertainties in lifetimes. We show that additional mechanisms that are responsible for radial transport are required to explain the dynamics of ≥40-keV electrons, and the inclusion of the radial diffusion rates that are typically assumed in radiation belt studies leads to a better agreement with the data. The overall effect of subauroral polarization streams on the electron phase space density profiles seems to be smaller than the uncertainties in other input parameters. This study is an initial step toward understanding the dynamics of these particles inside the geostationary orbit.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Mechanisms Behind the Extratropical Stratiform Low-Cloud Optical Depth Response to Temperature in ARM Site Observations

Ground-based observations from three middle- and high-latitude sites managed by the U.S. Department of Energy's Atmospheric Radiation Measurement (ARM) program are used to determine the sensitivity of the low-cloud optical depth to temperature and to test whether observations support mechanisms previously proposed to affect the optical depth feedback. Analysis of cloud optical depth retrievals support previous satellite findings that the optical depth decreases or stays constant with increases in temperature when the cloud is warm but increases when the cloud is cold. The cloud liquid water path sensitivity to warming largely explains the optical depth sensitivity at all sites.Mechanisms examined in this study involve the temperature dependence of (a) the moist-adiabatic lapse rate, (b) cloud phase partitioning, (c) drying efficiency of cloud top mixing, (d) cloud top inversion strength,and (e) boundary layer decoupling. Mechanism (a) is present across all clouds and explains 30% to 50%of the increase in liquid water path with warming at temperatures below 0°C. However, the cloud's adiabaticity, the ratio between the liquid water path and its theoretical maximum, is at least as important and determines how the liquid water path sensitivity to temperature varies with temperature. At temperatures below 0°C, the adiabaticity increases with warming, and the data support mechanism (b).At warmer temperatures, the adiabaticity decreases with warming, overwhelming mechanism (a) and resulting in the liquid water path decreasing with warming. This adiabaticity decrease arises primarily because of mechanism (d), and to a lesser degree because of mechanism (e). No evidence is found supporting mechanism (c)

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Antarctic Sea Ice Expansion, Driven by Internal Variability, in the Presence of Increasing Atmospheric CO2

A number of physically-based hypotheses have been proposed to explain the surprising expansion of Antarctic sea ice area (SIA) over the satellite era (1979 to 2015). Here, we use a fully-coupled state-of-the-art global climate model to show that internal variability alone can produce such multidecadal periods of Antarctic SIA expansion even as atmospheric CO2 increases at observed rates and the planet warms. When our model is started from a relatively warm Southern Ocean state, Antarctic SIA sometimes (in one of three ensemble members) expands over multidecadal time scales at a rate comparable to that over the satellite era. SIA expansion occurs concurrently with rising atmospheric CO2 and warming global surface temperatures, and SIA trends by region and sector resemble those over the satellite era. Our results suggest that internal variability, particularly on long time scales over the Southern Ocean, may suffice to explain Antarctic SIA expansion over the satellite era.

Singh, Hansi AK↗
DOE OSTI2019

Three-Dimensional Magnetic Reconnection With a Spatially Confined X-Line Extent: Implications for Dipolarizing Flux Bundles and the Dawn-Dusk Asymmetry

Using 3-D particle-in-cell simulations, we study magnetic reconnection with the X-line being spatially confined in the current direction.We include thick current layers to prevent reconnection at two ends of a thin current sheet that has a thickness on an ion inertial ($d_i$) scale. The reconnection rate and outflow speed drop significantly when the extent of the thin current sheet in the current direction is $≲ O$(10$d_i$). When the thin current sheet extent is long enough, we find that it consists of two distinct regions; a suppressed reconnecting region (on the ion-drifting side) exists adjacent to the active region where reconnection proceeds normally as in a 2-D case with a typical fast rate value ≃ 0.1. The extent of this suppression region is $≃ O$(10$d_i$), and it suppresses reconnection when the thin current sheet extent is comparable or shorter. The time scale of current sheet thinning toward fast reconnection can be translated into the spatial scale of this suppression region, because electron drifts inside the ion diffusion region transport the reconnected magnetic flux, which drives outflows and furthers the current sheet thinning, away from this region. This is a consequence of the Hall effect in 3-D. While the existence of this suppression region may explain the shortest possible azimuthal extent of dipolarizing flux bundles at Earth, it may also explain the dawn-dusk asymmetry observed at the magnetotail of Mercury, which has a global dawn-dusk extent much shorter than that of Earth.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Understanding Monsoonal Water Cycle Changes in a Warmer Climate in E3SMv1 Using a Normalized Gross Moist Stability Framework

Abstract One of the grand challenges of climate science is understanding the changes of the tropical rain belts and monsoon systems owing to CO 2 ‐induced warming. A promising path forward links the fluxes of energy and moisture to tropical circulation features. To this end, we make use of the Energy Exascale Earth System Model version 1, where the divergence of moist static energy and moisture have been calculated online, and employ a normalized gross moist stability (NGMS) diagnostic framework to understand the linkages between changes in the flow of energy and moisture within the monsoons. We focus on the Asian Summer Monsoon system and utilize a series of atmosphere‐land and atmosphere‐land‐ocean simulations to understand the connection between fluxes and monsoons. Uncoupled simulations with prescribed sea surface temperatures indicate that decreases in NGMS over land are important in explaining precipitation increases in response to both sea surface temperature and CO 2 increases. In fully coupled experiments, NGMS decreases remain an important contributor to the increase in P‐E, but the coupled simulations highlight the importance of consistent ocean and land responses in interpreting the monsoon changes. This study indicates that transient eddy fluxes play an important role in NGMS decreases and that a time‐mean view of the monsoon circulations is insufficient to quantify the link between future changes in the fluxes of energy and moisture. Compensation between dynamic and thermodynamic components of vertical moist static energy advection occurs, with the thermodynamic contribution dominating. The compensation is shown to be sensitive to relative humidity, with higher relative humidity leading to a stronger thermodynamic component.

Harrop, Bryce E.↗
DOE OSTI2019

Disentangling the Effects of Temperature, Moisture, and Substrate Availability on Soil CO 2 Efflux

Soil respiration ($R_s$), the largest carbon emission flux in ecosystems, is usually modeled as an empirically parameterized function of temperature, and sometimes water availability. The likely contribution by other factors, such as carbohydrate substrate supply from photosynthesis, has been recognized, but modeling capacity to use this information is limited. Wavelet transformations of the residuals of a seasonal Q 10 temperature response model indicated structure at different temporal scales. In this work, we hypothesize that this indicates the lack of explicit representation of relevant processes in the models. Using cross-spectral analysis, we found that time series of photosynthetically active radiation explained most of the diurnal variation, temperature, explained variability at multiple time scales (diurnal-synoptic), whereas volumetric soil water content correlated with variability in Rs at scales 15-30 days. The results suggest that the time domains of influence for different driving variables of $R_s$ are discrete, and largely nonoverlapping, and represent functional relationships between soil biological activity and its constraints. Analysis of phase angles showed that $R_s$ lagged photosynthetically active radiation by 1.5-3.0 hr. As this time lag was the same in both young and mature trees, with more than fivefold difference in transport distances, we hypothesize that this finding adds to the body of literature that support the pressure-concentration-wave model of carbohydrate availability in plants.

54 ENVIRONMENTAL SCIENCES↗