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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 1,405 records · Page 78
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Solvent effects in the liquid phase hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst model

Solvation effects of liquid water and 1,4-dioxane have been studied from first principles for the hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst surface model. Microkinetic reaction models have been developed for various reaction environments to study the effects of solvents on the reaction mechanism. Our models predict that in all reaction environments, decarbonylation pathways are favored over decarboxylation pathways. However, in the presence of liquid water the decarboxylation mechanism is facilitated due to solvent stabilization of the dehydrogenated derivatives of propionate. Altogether, the activity of Pd(1 1 1) is one order of magnitude lower in water than in 1,4-dioxane where we predict the activity to be very similar to the vapor phase. The decrease in Pd(1 1 1) activity due to liquid water can be traced back to the Pd surface being more crowded and propanoyl–methoxy type dissociations becoming more difficult. Propanoyl–methoxy type dissociations also become more rate controlling in liquid water than the dehydrogenation steps that are most rate controlling in 1,4-dioxane and in the vapor phase.

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

Identification and quantification of distinct active sites in Hf-Beta zeolites for transfer hydrogenation catalysis

Despite the significant progress made in characterizing different framework heteroatom sites that exist in Lewis acidic zeolites with probe molecule adsorption and spectroscopy, methods to reliably quantify site counts remain indefinite and have been primarily limited to Sn and Ti Lewis acid sites. Here, methods to quantify framework Lewis acidic Hf 4+ sites in zeolite Beta (Hf-Beta) with two Lewis base titrants (pyridine, deuterated acetonitrile) were developed using infrared (IR) spectroscopy. Lewis acid site counts for Hf-Beta zeolites were validated by measuring integrated molar extinction coefficients (IMECs; ε, cm μmol –1 ) on Sn-Beta zeolites using identical Lewis base titrants to benchmark site counts with established literature procedures to quantify Lewis acid sites in Beta zeolites from IR spectra. Highlighting the importance of benchmarking active site counts against well-established experimental protocols, IMECs of CD 3 CN bound to open (ε(Sn; 2316 cm –1 ): 1.80 ± 0.25) and closed (ε(Sn; 2308 cm –1 ): 3.76 ± 0.33) Sn sites were ~1.8x larger than those previously reported while total Lewis acid site counts agreed with those measured by pyridine (ε(Sn; 1451 cm –1 ): 1.58 ± 0.16) on six different Sn-Beta zeolites. IMECs measured for IR peaks reflecting pyridine bound to Lewis acidic Hf sites (ε(Hf; 1448 cm –1 ): 1.54 ± 0.21) and CD 3 CN bound to open (ε(Hf; 2313 cm –1 ): 2.40 ± 0.22) and closed (ε(Hf; 2307 cm –1 ): 3.55 ± 0.41) Hf sites, gave similar counts for the total number of Lewis acidic sites across six Hf-Beta zeolites (Si/Hf = 100–413). Consistent with previous reports with Sn-Beta catalysts where open Sn sites are responsible for catalytic turnover, apparent first and zero-order MPVO rate constants (0.01–1 M cyclohexanone in 2-butanol; per total Hf, 373 K) correlated with the total number of open Hf sites, per total Hf, but not with the total number of closed Hf sites or total Lewis acid site counts. Measured initial MPVO rates (0.1 M cyclohexanone in 2-butanol, per open Hf, 373 K) were ~25x higher on hydrophobic Hf-Beta-F than on hydrophilic Hf-Beta-OH zeolites. Overall, the apparent first-order MPVO rate constants (2-butanol solvent, per open Hf, 373 K) were ~6x higher on Hf-Beta-F than on Hf-Beta-OH zeolites. The characterization methods reported here enable normalization of MPVO turnover rates on Sn- and Hf-Beta zeolites by their number of open sites. Finally, this enables performing quantitative rate comparisons across Lewis acid zeolites of varying active site identity, solvation, and pore topology used in liquid-phase catalysis.

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

Effect of temperature on the complexation of NpO 2 + with benzoic acid: Spectrophotometric and calorimetric studies

The equilibrium constants of the 1:1 NpO2+/benzoate complex were determined by spectrophotometric titrations at variable temperatures (T = 283 to 343 K) and the ionic strength of 1.05 mol · kg-1. The enthalpy of complexation at T = 298 K was determined by microcalorimetric titrations. Similar to other monocarboxylates, benzoate forms a weak complex with NpO2+ and the complexation is strengthened as the temperature is increased. The complexation is endothermic and is entropy-driven. The enhancement of the complexation at elevated temperatures is primarily attributed to the increasingly larger entropy gain when the water molecules are released from the highly-ordered solvation spheres of NpO2+ and benzoate to the bulk solvent where the degree of disorder is higher at higher temperatures. The spectroscopic features of the Np(V)/benzoate system, including the effect of temperature on the absorption bands, are discussed in terms of ligand field splitting and a thermal expansion mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Deuteron off-resonance rotating frame relaxation for the characterization of slow motions in rotating and static solid-state proteins

Here, we demonstrate the feasibility of deuterium solid-state NMR off-resonance rotating frame relaxation measurements for studies of slow motions in biomolecular solids. The pulse sequence, which includes adiabatic pulses for magnetization alignment, is illustrated for static and magic-angle spinning conditions away from rotary resonances. We apply the measurements for three systems with selective deuterium labels at methyl groups: a) a model compound, Fluorenylmethyloxycarbonyl methionine-D 3 amino acid, for which the principles of the measurements and corresponding motional modeling based on rotameric interconversions are demonstrated; b) amyloid-β 1-40 fibrils labeled at a single alanine methyl group located in the disordered N-terminal domain. This system has been extensively studied in prior work and here serves as a test of the method for complex biological systems. The essential features of the dynamics consist of large-scale rearrangements of the disordered N-terminal domain and the conformational exchange between the free and bound forms of the domain, the latter one due to transient interactions with the structured core of the fibrils. and c) a 15-residue helical peptide which belongs to the predicted α-helical domain near the N-terminus of apolipoprotein B. The peptide is solvated with triolein and incorporates a selectively labeled leucine methyl groups. The method permits model refinement, indicating rotameric interconversions with a distribution of rate constants.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Polysulfide-incompatible additive suppresses spatial reaction heterogeneity of Li-S batteries

Rational electrolyte engineering for practical pouch cells remains elusive because the correlation between the cathode/solid-electrolyte interphase layer and cell-level reaction behavior is poorly understood. Here, by combining multiscale characterization and computational modeling, we show that—counter to the conventional perception of polysulfide-incompatible additives—the spontaneous reaction of sparingly solvated polysulfides with Lewis acid additives (LAAs) can induce in situ formation of a homogeneous interphase on thick and tortuous S cathode. Multiscale synchrotron X-ray characterization consistently affirms that such interface design could effectively eliminate the notorious problems of polysulfide shuttle and lithium corrosion and, more importantly, provide an interconnected “ion transport highway” to alleviate the uneven ion transport within the tortuous S cathode. Hence, this design dramatically reduces the reaction heterogeneity of lithium-sulfur (Li-S) pouch cells under lean electrolyte conditions. Further, this work resolves controversy around the role of polysulfide-incompatible additives in high-energy Li-S pouch cells and highlights the importance of suppressing reaction heterogeneity for practical batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A low-cost, fluorine-free electrolyte for improved sodium batteries

Sodium batteries are an attractive alternative to lithium-ion technologies due to sodium’s lower cost and natural abundance—over 1,000 times greater than lithium, comprising approximately 2.4% of the Earth’s crust. However, most current electrolytes rely on fluorine-containing components, which raise economic and environmental concerns. This study explores fluorine-free, borate-based electrolytes that offer improved cycling stability and significant cost and sustainability benefits. We demonstrate stable sodium metal stripping and plating on aluminum foil, enabling anode-free cell configurations with over 50% capacity retention after 700 cycles. Spectroscopic and electrochemical analyses reveal the effects of solvents and salt composition on solvation, ionic conductivity, and oxidative stability. In full-cell configurations, the fluorine-free electrolyte maintains more than 98% capacity retention after 400 cycles. Furthermore, these findings represent a critical step toward the development of cost-effective, environmentally friendly, and high-performance sodium battery systems suitable for future electrification.

anode-free sodium batteries↗
DOE OSTI2010

Synthesis and characterization of Pd(0), PdS, and Pd-PdO core-shell nanoparticles by solventless thermolysis of a Pd-thiolate cluster

Colloids of palladium nanoparticles have been prepared by the solvated metal atom dispersion (SMAD) method. The as-prepared Pd colloid consists of particles with an average diameter of 2.8{+-}0.1 nm. Digestive ripening of the as-prepared Pd colloid, a process involving refluxing the as-prepared colloid at or near the boiling point of the solvent in the presence of a passivating agent, dodecanethiol resulted in a previously reported Pd-thiolate cluster, [Pd(SC{sub 12}H{sub 25}){sub 2}]{sub 6} but did not render the expected narrowing down of the particle size distribution. Solventless thermolysis of the Pd-thiolate complex resulted in various Pd systems such as Pd(0), PdS, and Pd-PdO core-shell nanoparticles thus demonstrating its versatility. These Pd nanostructures have been characterized using high-resolution electron microscopy and powder X-ray diffraction methods. - Graphical abstract: Solventless thermolysis of a single palladium-thiolate cluster affords various Pd systems such as Pd(0), Pd-PdO core-shell, and PdS nanoparticles demonstrating the versatility of the precursor and the methodology.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg{sup 2+}), relative to lithium-ion (Li{sup +}) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg{sup 2+}, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A stable graphite electrode in superconcentrated LiTFSI-DME/DOL electrolyte and its application in lithium-sulfur full battery

Graphical abstract: In superconcentrated ether-based solutions, the formed SEI film inhibits electrolyte decomposition and graphite exfoliation caused by co-intercalation of solvents. Thus, reversible lithium intercalation and de-intercalation at a graphite electrode has been realized. - Highlights: • Prelithiated graphite anodes are coupled with sulfur composite cathodes to form a Li–S full cell in superconcentrated LiTFSI-DME/DO electrolyte. • The introduced superconcentrated ether-based electrolyte permits reversible lithium intercalation and de-intercalation at a graphite electrode. • The assembled Li–S full battery exhibits better cycle performance and coulombic efficiencies. - Abstract: Herein, prelithiated graphite anodes are coupled with sulfur composite cathodes to form a Li–S full cell in superconcentrated ether electrolyte. This novel system is effective in avoiding sever corrosion of Li-metal anode and significantly improving the safety of present Li–S cell, owing to the replacement of Li-metal anode with graphite. The introduced superconcentrated ether electrolyte has a unique networking structure of Li cations and TFSI anions with Li{sup +}-solvating DME/DOL solvents, which is conducive to form a stable TFSI-derived surface film on the graphite electrode. The stable and dense TFSI-derived film inhibits further electrolyte decomposition and graphite exfoliation caused by co-intercalation of solvents, allowing reversible lithium intercalation and de-intercalation at a graphite electrode. Besides, the severe polysulfides shuttle is also suppressed by the concentrated ether-based solutions. Consequently, the assembled graphite-sulfur full battery retains outstanding capacity of 686 mAh g{sup −1}{sub sulfur} at 0.1C rate after 105 cycles, along with high Coulombic efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The effects of filamentary Ni, graphene and lithium amide (LiNH2) additives on the dehydrogenation behavior of mechano-chemically synthesized crystalline manganese borohydride (Mn(BH4)2) and its solvent filtration/extraction

Highlights: • Effect of graphene, filamentary Ni and LiNH{sub 2} on the synthesis of Mn(BH{sub 4}){sub 2} investigated. • Mechanical dehydrogenation observed for filamentary Ni and LiNH{sub 2} but not for graphene. • All additives suppressed the release of B{sub 2}H{sub 6} during thermal decomposition of Mn(BH{sub 4}){sub 2} with filamentary Ni being the strongest suppressor. • The LiNH{sub 2} additive reduced the apparent activation energy for dehydrogenation to 44.9 ± 4.3 kJ/mol. • After solvent filtration and extraction of the (Mn(BH{sub 4}){sub 2}/LiCl) sample, a dimetallic hydride [{Li(Et_2O)_2}Mn{sub 2}(BH{sub 4}){sub 5}] was found. - Abstract: Dehydrogenation properties of mechano-chemically synthesized crystalline Mn(BH{sub 4}){sub 2} hydride without and with ultrafine filamentary carbonyl nickel (Ni), graphene and LiNH{sub 2} were investigated. It is reported for the first time that all additives suppressed the release of B{sub 2}H{sub 6} with the filamentary Ni additive being the most effective suppressor of B{sub 2}H{sub 6}. In DSC, the decomposition peak of Mn(BH{sub 4}){sub 2} was endothermic. The estimated apparent activation energy for isothermal dehydrogenation was dramatically reduced to 44.9 ± 4.3 kJ/mol for the 5 wt.% LiNH{sub 2} additive from about 76–81 kJ/mol range for the additive-free sample and 5 wt.% filamentary Ni and graphene additives. The most striking finding, that has never been reported in the literature, is that the process of solvent filtration and extraction of the mechano-chemically synthesized (Mn(BH{sub 4}){sub 2}/LiCl) sample, resulted in the crystallization of a dimetallic borohydride solvate [{Li(Et_2O)_2}Mn{sub 2}(BH{sub 4}){sub 5}] instead of crystalline Mn(BH{sub 4}){sub 2}. Its dehydrogenation behavior was investigated isothermally and by TGA/DSC.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Influence of fixed charge concentration and water uptake on ion sorption in AMPS/PEGDA membranes

Water content and charge density strongly influence ion sorption in charged membranes. However, isolating the individual effect of each parameter on ion sorption can be difficult due to experimental challenges associated with independently controlling these two variables during membrane synthesis. This frustrates development and validation of fundamental models and structure/property relationships. In this study, three series of uncharged and negatively charged hydrogel membranes were prepared using poly(ethylene glycol) diacrylate (PEGDA) as a cross-linker and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an ionic monomer. Here, water content and charge density were controlled by varying AMPS content and PEGDA chain length. Ion sorption in these materials was measured using aqueous NaCl solutions at concentrations ranging from 0.01 to 1.0 M. At constant charge density, salt sorption increased as water content increased. At fixed water content, salt sorption decreased as charge density increased. Salt sorption in membranes with the highest water content and charge density was predicted using the Donnan/Manning model, which accounts for solution and membrane phase thermodynamic non-idealities. However, this approach could not predict sorption in weakly charged and uncharged membranes, presumably due to additional membrane phase thermodynamic non-idealities associated with ion solvation and uncharged polymer segments.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ab initio metadynamics calculations reveal complex interfacial effects in acetic acid deprotonation dynamics

Acid-base reactions play a central role in solution chemistry, with carboxylic acids being particularly important in atmospheric chemical processes. In this work, we harness metadynamics calculations with Born-Oppenheimer molecular dynamics (BOMD) simulations to understand deprotonation dynamics of acetic acid (CH 3 COOH) in both bulk and air-water interfacial environments. Collective variables are carefully chosen in our well-tempered metadynamics simulations to capture the deprotonation process in various aqueous configurations. Herein, our findings show that the free energy barrier for deprotonation of acetic acid at the air-water interface is lower than in the bulk, in accordance with the available experimental data. Furthermore, our well-tempered metadynamics calculations suggest that the variations in free energy are primarily due to intricate solvation shell effects.

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

Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

The speciation and reactivity of aqueous salt solutions are important for a wide variety of applications. However, application of this information is inhibited by broad disagreement about composition, mechanisms, and structure in concentrated solutions especially. Here, neutron diffraction with isotopic substitution measurements on aqueous zinc chloride solutions are used to calibrate molecular dynamics simulations that include effective electronic polarization. This allows us to probe the origin of speciation and reactivity of zinc chloride-water ion complexes, ZnCl x (H 2 O) y 2-x (x ≤ 4 and y ≤ 6), by comparing the reactivity of species in concentrated (4.5 m) and dilute (0.01 m) conditions. Within the concentrated solution, it is found that the extended solvation environment is dominated by solvent-separated ion complexes whose presence increases the free energy of activation for interconversion of species while simultaneously enhancing their thermodynamic stability. This concentration-dependent reactivity and stability suggests that other reactions, such as the nucleation of solid phases, will also be affected.

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

Actinides in complex reactive media: A combined ab initio molecular dynamics and machine learning analytics study of transuranic ions in molten salts

The predominant ionic chemistry and the similarity in ionic radius of actinides make it very difficult to structurally distinguish them in liquids. In this work, while ab initio molecular dynamics shows that the f-states clearly affects the electronic properties, their impact on structural properties is not obvious. For the series of trivalent actinides U 3+ , Pu 3+ , Cm 3+ , Cf 3+ , Fm 3+ in molten NaCl and FLiBe, actinide ligand bonds have a higher degree of covalency in NaCl (than in FLiBe), and a higher degree of ionicity in FLiBe. Furthermore, a machine learned classification model can distinguish atomic environments of chemically similar actinides, as long as atoms beyond the first solvation shells are considered. Our work shows that only two types of descriptors are necessary to account for all the fluctuations in heavy metal/molten salt mixtures: The first descriptor represents the electronic state of the heavy metal, while the second encompasses the local coordination environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Design of enhanced porous organic cage solubility in Type 2 porous liquids

Decreasing cost of technologies for direct air capture of carbon can be achieved through the design of new materials with high CO 2 selectivity that can be incorporated into existing industrial processes. An emerging class of materials for these applications are porous liquids (PLs). PLs are mixtures of porous hosts and solvents with intrinsic porosity due to steric exclusion of solvent from inside the porous host. It is currently unknown how solvent -porous host interactions affect porous host solubility in the bulk solvent. Here, in this study, density functional theory simulations were used to investigate interactions between nine solvents and a CC13 porous organic cage (POC). Calculations identified that solvent molecules were the most stable when placed either inside the CC13 POC or in the pore window compared to interfacial binding sites. Structural changes to the CC13 POC correlated with reported experimental solubilities, including expansion of the CC13 POC with solvent molecule infiltration and expansion or contraction of the pore window. Based on these results, new PL design guidelines should include compositions with (1) high concentrations of POCs with flexible cage structures that can expand when solvated and (2) solvent molecule-POC combinations that contract the pore window during solvent molecule-host binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Unraveling local structures of Salt-in-Water and Water-in-Salt electrolytes via ab initio molecular dynamics

Water-in-salt electrolytes (WiSE) are attractive for electrochemical energy storage applications owing to their wide electrochemical stability windows and inherent safety. The high concentration of salts is widely known to suppress the decomposition of water, which otherwise limits the stability of conventional aqueous salt-in-water electrolytes (SiWE). Nevertheless, the microstructural features of WiSE that lead to this enhanced stability have not yet been fully elucidated. In this work, ab initio molecular dynamics simulations were performed to study the energetic, structural, and spectroscopic properties of LiTFSI SiWE and WiSE solutions. A detailed mapping of water-water and water-anion hydrogen bonding and cation–anion electrostatic interactions is reported for both electrolytes. Structural features are presented in terms of both radial and spatial distribution functions. Analysis of IR and vibrational power spectra reveal key differences in the intermolecular interactions in SiWE and WiSE that arise from modified solvation shell structures. Finally, the results obtained herein reveal the most important structural and spectroscopic differences between the electrolytes in normal and superconcentrated concentrations.

36 MATERIALS SCIENCE↗