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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 OSTI2011

The Role of Hydrophobic Surfaces in Altering Water-Mediated Peptide-Peptide Interactions in an Aqueous Environment

Using Born-Oppenheimer molecular dynamics within the density functional framework, we calculated the effective force acting on water-mediated peptide-peptide interaction between antiparallel β-sheets in an aqueous environment and also in the vicinity of a hydrophobic surface. From the magnitude of the effective force (corresponding to the slope of the free energy as a function of the inter-peptide distance) and its sign (a negative value indicating an effective attraction whereas a positive value an effective repulsion) we can elucidate the fundamental differences of the water-mediated peptide-peptide interactions in those two environments. The computed effective forces indicate that the water-mediated interaction between peptides in an aqueous environment is attractive in the range of inter-peptide distance d=7-8 Å when hydrophobic surfaces are not nearby. Due to the stabilization of the water molecules bridging between the two β-sheets, a free energy barrier exists between the direct and indirect (water-mediated) inter-peptide interactions. However, when the peptides are in the proximity of hydrophobic surfaces, this free energy barrier decreases because the hydrophobic surfaces enhance the inter-peptide attraction by the destabilization and ease-to-libration of the bridging water molecules between them. This work was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, US Department of Energy. Battelle operates the Pacific Northwest National Laboratory for the U.S. Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Understanding the Rates and Molecular Mechanism of Water-Exchange around Aqueous Ions Using Molecular Simulations

Solvation processes occurring around aqueous ions are of fundamental importance in physics, chemistry, and biology. Over the past few decades, several experimental and theoretical studies were devoted to understanding ion solvation and the processes involved in it. In this article, we present a summary of our recent efforts that, through computer simulations, focused on providing a comprehensive understanding of solvent-exchange processes around aqueous ions. To accomplish these activities, we have looked at the mechanistic properties associated with the water-exchange process, such as potentials of mean force, time-dependent transmission coefficients, and the corresponding rate constants using transition rate theory, the reactive flux method, and Grote-Hynes treatments of the dynamic response of the solvent. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the U.S. Department of Energy (DOE) funded this work. Battelle operates Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.

Annapureddy, Harsha V.↗
DOE OSTI2014

NO3- Coordination in Aqueous Solutions by 15 N/ 14 N and 18O/natO Isotopic Substitution: What Can We Learn from Molecular Simulation?

We explore the deconvolution of the water-nitrate correlations by the first-order difference approach involving neutron diffraction of heavy- and null-aqueous solutions of KNO 3 under 14 N 15 N and natON 18 ON substitutions to achieve a full characterization of the first water coordination around the nitrate ion. For that purpose we performed isobaric-isothermal simulations of 3.5m KNO 3 aqueous solutions at ambient conditions to generate the relevant radial distribution functions (RDF) required in the analysis (a) to identify the individual partial contributions to the total neutron weighted distribution function, (b) to isolate and assess the contribution of NO 3 -!K + pair formation, (c) to test the accuracy of the NDIS-based coordination calculations and XRDbased assumptions, and (d) to describe the water coordination around both the nitrogen and oxygen sites of the nitrate ion.

14N 15N and natON 18ON isotopic substitution↗
DOE OSTI2011

Aqueous NaCl and CsCl Solutions Confined in Crystalline Slit-Shaped Silica Nanopores of Varying Degree of Protonation

All-atom molecular dynamics simulations were conducted to study the dynamics of aqueous electrolyte solutions confined in slit-shaped silica nanopores of various degrees of protonation. Five degrees of protonation were prepared by randomly removing surface hydrogen atoms from fully protonated crystalline silica surfaces. Aqueous electrolyte solutions containing NaCl or CsCl salt were simulated at ambient conditions. In all cases, the ionic concentration was 1 M. The results were quantified in terms of atomic density distributions within the pores, and the self-diffusion coefficient along the direction parallel to the pore surface. We found evidence for ion-specific properties that depend on ion-surface, water-ion, and only in some cases ion-ion correlations. The degree of protonation strongly affects the structure, distribution, and the dynamic behavior of confined water and electrolytes. Cl - ions adsorb on the surface at large degrees of protonation, and their behavior does not depend significantly on the cation type (either Na + or Cs + ions are present in the systems considered). The cations show significant ion-specific behavior. Na + ions occupy different positions within the pore as the degree of protonation changes, while Cs + ions mainly remain near the pore center at all conditions considered. For a given degree of protonation, the planar self-diffusion coefficient of Cs + is always greater than that of Na + ions. The results are useful for better understanding transport under confinement, including brine behavior in the subsurface, with important applications such as environmental remediation.

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

Structure of Biodegradable Films at Aqueous Surfaces: X-ray Diffraction and Spectroscopy Studies of Polylactides and Tyrosine-Derived Polycarbonates

Three representative polymers of increasing modulus, poly(d,l-lactic acid), PDLLA, poly(desaminotyrosyl-tyrosine ethyl ester carbonate), PDTEC, and the same polymer with iodinated DTE segments, PI2DTEC, were characterized by surface-pressure versus area (Π–A) isotherms and surface sensitive X-ray diffraction techniques. Films of 10–100 Å thickness were prepared for these studies by spreading dilute polymer solutions at air–water interfaces. The general properties of the isotherms and the Flory exponents, determined from the isotherms, vary in accordance with the increasing modulus of PDLLA, PDTEC, PI2DTEC, respectively. The analysis of in situ X-ray reflectivity and grazing incidence X-ray diffraction (GIXD) measurements from films at aqueous surfaces provides a morphological picture that is consistent with the modulus of the polymers, and to a large extent, with their packing in their dry-bulk state. Large absorption of X-rays by iodine enabled X-ray spectroscopic studies under near-total-reflection conditions to determine the iodine distribution in the PI2DTEC film and complement the structural model derived from reflectivity and GIXD. These structural studies lay the foundation for future studies of polymer–protein interactions at aqueous interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Bacteria establish an aqueous living space in plants crucial for virulence

High humidity has a strong influence on the development of numerous diseases affecting the above-ground parts of plants (the phyllosphere) in crop fields and natural ecosystems, but the molecular basis of this humidity effect is not understood. Previous studies have emphasized immune suppression as a key step in bacterial pathogenesis. We show that humidity-dependent, pathogen-driven establishment of an aqueous intercellular space (apoplast) is another important step in bacterial infection of the phyllosphere. Bacterial effectors, such as Pseudomonas syringae HopM1, induce establishment of the aqueous apoplast and are sufficient to transform non-pathogenic P. syringae strains into virulent pathogens in immunodeficient Arabidopsis thaliana under high humidity. Arabidopsis quadruple mutants simultaneously defective in a host target (AtMIN7) of HopM1 and in pattern-triggered immunity could not only be used to reconstitute the basic features of bacterial infection, but also exhibited humidity-dependent dyshomeostasis of the endophytic commensal bacterial community in the phyllosphere. These results highlight a new conceptual framework for understanding diverse phyllosphere–bacterial interactions.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L -1 ) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI 2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L -1 at the solubility limit of ZnI 2 in water (~7 M). We demonstrate charge and discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI 2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI 2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.

25 ENERGY STORAGE↗
DOE OSTI2020

Enabling safe aqueous lithium ion open batteries by suppressing oxygen reduction reaction

Abstract Due to the non-flammable nature of water-based electrolytes, aqueous lithium-ion batteries are resistant to catching fire. However, they are not immune to the risk of explosion, since the sealing structure adopted by current batteries limits the dissipation of heat and pressure within the cells. Here, we report a safe aqueous lithium-ion battery with an open configuration using water-in-salt electrolytes and aluminum oxide coated anodes. The design can inhibit the self-discharge by substantially suppressing the oxygen reduction reaction on lithiated anodes and enable good cycle performance over 1000 times. Our study may open a pathway towards safer lithium-ion battery designs.

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

Reactive CO 2 capture via controlled amine speciation in non-aqueous electrolytes

Current efforts to integrate CO 2 capture and electrochemical conversion (reactive capture) are often performed under aqueous conditions, resulting in undesired hydrogen evolution and reliance on precious metal catalysts and pure CO 2 streams. Here, in this study, we explore reactive capture in aprotic media. By shifting the amine–CO 2 adduct speciation to carbamic acid (instead of carbamate) in dimethyl sulfoxide, we increased CO 2 uptake threefold compared with an aqueous medium, suppressing hydrogen evolution and supporting a 78% Faradaic efficiency towards CO over an earth-abundant zinc catalyst. Under simulated high-oxygen-content flue gas (17% CO 2 , 17% O 2 , 66% N 2 ), we also obtained up to 43% CO Faradaic efficiency over multiple capture–conversion cycles. Our findings showcase the confluence of reactant speciation, electrolyte composition and electrocatalyst design in enabling selective and active electrochemical transformations.

Gomes, Reginaldo J. [Univ. of Chicago, IL (United ↗
DOE OSTI2018

29Si NMR of aqueous silicate complexes at gigapascal pressures

Abstract Geochemists have models to predict solute speciation and mineral equilibria in aqueous solutions up to 1200 °C and 6 GPa. These models are useful to uncover reaction pathways deep in the Earth, though experimental confirmation is extremely difficult. Here we show speciation changes among aqueous silicate complexes to pressures of 1.8 GPa through use of a high-pressure solution-state NMR probe. The radiofrequency circuit uses a microcoil geometry that is coupled with a piston-cylinder pressure cell to generate and maintain these high pressures. The 1.8 GPa pressure corresponds to pressures reached at the lower crust or upper mantle. Although these experiments are limited to ambient temperature, we show that the increased pressure affects complexation and oligomerization reactions by eliminating bulk waters and that the pressure effects are completely reversible.

58 GEOSCIENCES↗
DOE OSTI2022

Multi-objective goal-directed optimization of de novo stable organic radicals for aqueous redox flow batteries

Abstract Advances in the field of goal-directed molecular optimization offer the promise of finding feasible candidates for even the most challenging molecular design applications. One example of a fundamental design challenge is the search for novel stable radical scaffolds for an aqueous redox flow battery that simultaneously satisfy redox requirements at the anode and cathode, as relatively few stable organic radicals are known to exist. To meet this challenge, we develop a new open-source molecular optimization framework based on AlphaZero coupled with a fast, machine-learning-derived surrogate objective trained with nearly 100,000 quantum chemistry simulations. The objective function comprises two graph neural networks: one that predicts adiabatic oxidation and reduction potentials and a second that predicts electron density and local three-dimensional environment, previously shown to be correlated with radical persistence and stability. With no hard-coded knowledge of organic chemistry, the reinforcement learning agent finds molecule candidates that satisfy a precise combination of redox, stability and synthesizability requirements defined at the quantum chemistry level, many of which have reasonable predicted retrosynthetic pathways. The optimized molecules show that alternative stable radical scaffolds may offer a unique profile of stability and redox potentials to enable low-cost symmetric aqueous redox flow batteries.

25 ENERGY STORAGE↗
DOE OSTI2013

Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions.

Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products.

Thoi, V Sara↗
DOE OSTI2013

Understanding ion-ion interactions in bulk and aqueous interfaces using molecular simulations

In addition to its scientific significance, the distribution of ions in the bulk and at aqueous interfaces also is very important for practical reasons. A quantitative description of the ionic distribution and how to describe interactions between them in different environments remain a challenge are the subjects of current debate. In this study, we found that interionic potentials of mean force (PMF) and interfacial properties are very sensitive to the ion-ion interaction potential models. Our computed Sr2+-Cl- PMF shows a no contact ion-pair state and a shallow solvent-separated ion-pair state. In addition, we were able to quantitatively capture the experimental x-ray reflectivity results of the aqueous salt interface of Sr2+-Cl- ion-pair system, and predict the reflectivity for Sr2+-Br- and Sr2+-I- systems. In this paper, we provide a detailed physical description of the interfacial structure of these systems.. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for DOE by Battelle.

Dang, Liem X↗
DOE OSTI2013

A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets

Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T , and solution water activity, a w , which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humidity (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, J het , to be uniquely expressed by T and a w , a result we term the aw based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, J het , frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A , and cooling rates, r , of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log 10 (J het ) values for the various IN types derived exclusively by T and a w , provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T , RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Finally, we demonstrate that ABIFM can be used to derive frozen fractions of droplets and ice particle production for atmospheric models of cirrus and mixed phase cloud conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Aqueous medium induced optical transitions in cerium oxide nanoparticles

Experimental and theoretical investigations were performed to investigate the effect of water on optical properties of nanoceria as a function of Ce3+ concentration. Theoretical studies based on density functional plane-wave calculations reveal that the indirect optical transitions in bare ceria nanoparticles are red-shifted with an increase in the concentration of Ce3+. However, ceria nanoparticles model with adsorbed water molecules show a blue shift in the indirect optical spectra under identical conditions. Direct optical transitions are almost independent of Ce3+ concentration but show a pronounced blue shift in the aqueous environment relative to the bare nanoparticles. The theoretical study is consistent with our experimental observation in difference of shift behaviour in bare and aqueous suspended ceria nanoparticles. This change from red- to blue-shift in indirect optical transitions is associated with the polarization effect of water molecules on f-electron states.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

An overview of selected current approaches to the characterization of aqueous inorganic clusters

This Perspective article highlights some of the traditional and non-traditional analytical tools that are currently used to characterize aqueous inorganic nanoscale clusters and polyoxometalate ions. The techniques discussed in this article include nuclear magnetic resonance spectroscopy (NMR), small angle X-ray scattering (SAXS), dynamic and phase analysis light scattering (DLS and PALS), Raman spectroscopy, and quantum mechanical computations (QMC). For each method we briefly describe how it functions and illustrate how these techniques are used to study cluster species in the solid state and in solution through several representative case studies. In addition to highlighting the utility of these techniques, we also discuss limitations of each approach and measures that can be applied to circumvent such limits as it pertains to aqueous inorganic cluster characterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium( iii ) chloride and hydrochloric acid solution

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3 –HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leads to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗