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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Highly efficient non-fullerene organic solar cells enabled by a delayed processing method using a non-halogenated solvent

The use of non-halogenated solvents is one of the important requirements for large-scale industry production of polymer solar cells (PSCs). However, the current high-performance PSCs are mostly obtained using halogenated solvents to ensure good solubility and morphology. In this work, we report high-performance PSCs processed using a halogen-free solvent (toluene), reaching an efficiency of 17.33%, which, to the best of our knowledge, is the highest value reported for PSCs processed from non-halogenated solvents. Importantly, we show a novel aggregation or “aging” process of the non-fullerene acceptor in the toluene solvent, which can be used to fine-tune the crystal size of the non-fullerene acceptor. As a result, we achieve an optimized nano-fibril like morphology of PM6:BTP-BO-4Cl by delaying the processing time. Furthermore ,this is conducive to charge dissociation and transport, and thus greatly improved device performance. This method is expected to be investigated further and applied to other PSC systems toward precise morphology optimization and performance improvements in the future.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Influence of solvent structure and hydrogen bonding on catalysis at solid–liquid interfaces

Solvent molecules interact with reactive species and alter the rates and selectivities of catalytic reactions by orders of magnitude. Specifically, solvent molecules can modify the free energies of liquid phase and surface species via solvation, participating directly as a reactant or co-catalyst, or competitively binding to active sites. These effects carry consequences for reactions relevant for the conversion of renewable or recyclable feedstocks, the development of distributed chemical manufacturing, and the utilization of renewable energy to drive chemical reactions. First, we describe the quantitative impact of these effects on steady-state catalytic turnover rates through a rate expression derived for a generic catalytic reaction (A → B), which illustrates the functional dependence of rates on each category of solvent interaction. Second, we connect these concepts to recent investigations of the effects of solvents on catalysis to show how interactions between solvent and reactant molecules at solid–liquid interfaces influence catalytic reactions. Furthermore, this discussion demonstrates that the design of effective liquid phase catalytic processes benefits from a clear understanding of these intermolecular interactions and their implications for rates and selectivities.

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

Modelling drug adsorption in metal–organic frameworks: the role of solvent

Solvent plays a key role in biological functions, catalysis, and drug delivery. Metal–organic frameworks (MOFs) due to their tunable functionalities, porosities and surface areas have been recently used as drug delivery vehicles. To investigate the effect of solvent on drug adsorption in MOFs, we have performed integrated computational and experimental studies in selected biocompatible MOFs, specifically, UiO-AZB, HKUST-1 (or CuBTC) and NH 2 -MIL-53(Al). The adsorption of three drugs, namely, 5-fluorouracil (5-FU), ibuprofen (IBU), and hydroxyurea (HU) were performed in the presence and absence of the ethanol. Our computational predictions, at 1 atmospheric pressure, showed a reasonable agreement with experimental studies performed in the presence of ethanol. We find that in the presence of ethanol the drug molecules were adsorbed at the interface of solvent and MOFs. Moreover, the computationally calculated adsorption isotherms suggested that the drug adsorption was driven by electrostatic interactions at lower pressures (<10 –4 Pa). Our computational predictions in the absence of ethanol were higher compared to those in the presence of ethanol. The MOF–adsorbate interaction (U HA ) energy decreased with decrease in the size of a drug molecule in all three MOFs at all simulated pressures. At high pressure the interaction energy increases with increase in the MOFs pore size as the number of molecules adsorbed increases. Thus, our research shows the important role played by solvent in drug adsorption and suggests that it is critical to consider solvent while performing computational studies.

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

Impact of the fluorination degree of ether-based electrolyte solvents on Li-metal battery performance

Electrolytes using fluorinated solvents have proven effective in improving the cycling life of Li-metal batteries, by forming a robust solid–electrolyte interphase through decomposition of anion and fluorinated solvent molecules. Herein, we modulated the fluorination degree of ether-based electrolyte solvents to investigate their performance in Li-metal batteries. Here, we tuned the fluorination degree by installing a monofluoro substituent on one ethoxy group of 1,2-diethoxyethane (DEE) and varying the fluorination degree on the other one, providing three fluorinated DEE solvent molecules (i.e., F1F0, F1F1 and F1F2) with a relatively low fluorination degree. All three electrolytes showed improved solvation strength and ionic conductivities compared with previous highly fluorinated DEE electrolytes while retaining good oxidative stability. A full cell test using the Li-metal anode and nickel-rich cathode revealed that a higher degree of fluorination is beneficial to the cycling performance, and the cycling stability follows F1F0 < F1F1 < F1F2. Specifically, F1F0 exhibited poor cycling stability due to its instability against both the anode and cathode. While F1F1 and F1F2 both showed good stability against the Li metal anode, their relative long-term oxidative stability was responsible for the distinct performance, in which the cycle numbers at 80% capacity retention for F1F1 and F1F2 were ~20 and ~80, respectively. Finally, we demonstrated that F1F2 was able to achieve 90 cycles before reaching 80% capacity retention in practical lithium iron phosphate (LFP) pouch cells. This work shows the importance of modulating the fluorination degree of electrolyte solvents, and this approach is suitable for various cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Solvent independent symmetry-breaking charge separation in terrylenediimide guanine-quadruplex nanoparticles

G-quadruplex assemblies are a promising tool for self-assembling π-stacked chromophore arrays to better understand their photophysics. We have shown that coupling a single guanine moiety to terrylenediimide (TDI) produces a structure (GTDI) that self-assembles in tetrahydrofuran (THF) into a nearly monodisperse guanine-quadruplex structure having 16 π-stacked layers (GTDI 4 ) 16 . The TDI surfaces were determined to have a high degree of cofacial overlap and underwent quantitative symmetry-breaking charge separation (SB-CS) upon photoexcitation. Here, we more deeply examine the relationship between solvent and aggregate formation and develop insights into structure–function relationships over a variety of solvent polarities and hydrogen-bonding capabilities. At high concentrations, GTDI assembles into guanine-quadruplex structures (GTDI 4 ) 16 in THF and toluene, as well as (GTDI 4 ) 9 in pyridine and benzonitrile. Here, transient absorption spectroscopy shows that SB-CS occurs in all solvents, regardless of their static dielectric constants, but the SB-CS yield is determined by structure. Solvent polarity independent SB-CS generation is also observed in GTDI films, where there is a complete absence of solvent.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Solvent structure and dynamics over Brønsted acid MWW zeolite nanosheets

In the liquid phase of heterogeneous catalysis, solvent plays an important role and governs the kinetics and thermodynamics of a reaction. Although it is often difficult to quantify the role of the solvent, it becomes particularly challenging when a zeolite is used as the catalyst. This difficulty arises from the complex nature of the liquid/zeolite interface and the different solvation environments around catalytically active sites. Here, we use ab initio molecular dynamics simulations to probe the local solvation structure and dynamics of methanol and water over MWW zeolite nanosheets with varying Brønsted acidity. We find that the zeolite framework and the number and location of the acid sites in the zeolite influence the structure and dynamics of the solvent. In particular, methanol is more likely to be in the vicinity of the aluminum (Al 3+ ) at the T4 site than at T1 due to easy accessibility. The methanol oxygen binds strongly to the Al at the T4 site, weakening the Al–O for the bridging acid site, which results in the formation of the silanol group, significantly reducing the acidity of the site. The behavior of methanol is in direct contrast to that of water, where protons can easily propagate from the zeolite to the solvent molecules regardless of the acid site location. Furthermore, our work provides molecular-level insights into how solvent interacts with zeolite surfaces, leading to an improved understanding of the catalytic site in the MWW zeolite nanosheet.

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

Isolating solvent–solute hydrogen bonding interactions via 2D IR solvation shell spectroscopy

The solvation shell around a solute is a fundamental feature of liquid-phase solutions, determining the behavior and properties of both the solute and the overall solution. Direct experimental measurements of the solvation shell properties are challenging due to the strong signals generated from the bulk solvent, which overwhelm the small contribution of the solvation shell. Here, we use ultrafast two dimensional infrared (2D IR) spectroscopy and intermolecular cross-peaks to isolate the IR absorption spectrum of methanol molecules in the solvation shell surrounding the solute N-methylacetamide. We demonstrate that the intermolecular coupling between the solvent and solute vibrations is indirectly mediated by a low-frequency hydrogen-bonding mode, suggesting an important mechanism for anharmonic coupling induced by hydrogen bonds. From the relative frequency shifts and cross-peak anisotropy, we find that methanol molecules surrounding N-methylacetamide form stronger and distinctly oriented hydrogen bonds than those in the bulk solvent. Here, we also compare these results with the solvent spectra of the solute N,N-dimethylacetamide to investigate how solute structural changes alter the solvation shell and the contribution of N–H hydrogen bond donation. Our results are supported by molecular dynamics simulations, which provide detailed insights into the hydrogen-bonding distributions. Through these results, we demonstrate 2D solvation shell spectroscopy to be a valuable method for investigating solvation structures and dynamics without interference from the bulk solvent.

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

Modeling the partitioning of amphiphilic molecules and co-solvents in biomembranes

We report amphiphilic co-solvents can have a significant impact on the structure, organization and physical properties of lipid bilayers. Describing the mutual impact of partitioning and induced structure changes is therefore a crucial consideration for a range of topics such as anesthesia and other pharmacokinetic effects, as well as microbial solvent tolerance in the production of biofuels and other fermentation products, where molecules such as ethanol, butanol or acetic acid might be generated. Small-angle neutron scattering (SANS) is a key method for studying lipid and polymer bilayer structures, with many models for extracting bilayer structure (thickness, area per lipid etc.) from scattering data in use today. However, the molecular details of co-solvent partitioning are conflated with induced changes to bilayer structure, making interpretation and modeling of the scattering curves a challenge with the existing set of models. To address this, a model of a bilayer structure is presented which invokes a two-term partition constant accounting for the localization of the co-solvent within the bilayer. This model was validated using a series of SANS measurements of lipid vesicles in the presence of the co-solvent tetrahydrofuran (THF), showing several strategies of how to deploy the two-parameter partition constant model to describe scattering data and extract both structure and partitioning information from the data. Molecular dynamics simulations are then used to evaluate assumptions of the model, provide additional molecular scale details and illustrate its complementary nature to the data fitting procedure. This approach results in estimates of the partition coefficient for THF in 1,2-dimyristoyl-sn-glycero-3-phosphocholine at 35°C, along with an estimate of the fraction of THF residing in the hydrophobic core of the membrane. The authors envision that this model will be applicable to a wide range of other bilayer/amphiphile interactions and provide the associated code needed to implement this model as a fitting algorithm for scattering data in the SasView suite.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions

In this study, we present results from explicit-solvent coarse-grained molecular dynamics (MD) simulations of fully charged, salt-free, and unentangled polyelectrolytes in semidilute solutions. The inclusion of a polar solvent in the model allows for a more physical representation of these solutions at concentrations, where the assumptions of a continuum dielectric medium and screened hydrodynamics break down. The collective dynamic structure factor of polyelectrolytes, S(q, t), showed that at q > q*, where q* = 2π/ξ is the polyelectrolyte peak in the structure factor S(q) and ξ is the correlation length, the relaxation time obtained from fits to stretched exponential was $\tau$ KWW ~ q -3 , which describes unscreened Zimm-like dynamics. This is in contrast to implicit-solvent simulations using a Langevin thermostat where $\tau$ KWW ~ q -2 . At q < q*, a crossover region was observed that eventually transitions to another inflection point $\tau$ KWW ~ q -2 at length scales larger than ξ for both implicit- and explicit-solvent simulations. The simulation results were also compared to scaling predictions for correlation length, ξ ~ c$-½\atop{p}$, specific viscosity, η sp ~ c$½\atop{p}$, and diffusion coefficient, D ~ c$0\atop{p}$, where c p is the polyelectrolyte concentration. The scaling prediction for ξ holds; however, deviations from the predictions for η sp and D were observed for systems at higher c p , which are in qualitative agreements with recent experimental results. This study highlights the importance of explicit-solvent effects in molecular dynamics simulations, particularly in semidilute solutions, for a better understanding of polyelectrolyte solution behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mapping Spatiotemporal Solvent Velocity from Measured Concentration Gradients in a Polarized Electrolyte

The electric-field induced motion of neutral species impedes the efficacy of electrochemical devices. By combining operando X-ray transmission measurements with continuum mechanics, we have developed a methodology for determining the velocity of neutral solvent molecules under an applied field. The X-ray transmission experiments were used to determine ion concentration profiles as a function of space and time in a polymer electrolyte. The unsteady state solvent mass balance equation was solved numerically with experimental concentration profiles to map spatiotemporal solvent velocities. We compare our experimentally derived results with predictions made with concentrated solution theory. We use the cation transference number as the only adjustable parameter to match experimental measurements of both concentration and solvent velocity. Our approach may be used to determine solvent velocity with any operando technique used to measure time-dependent ion concentration profiles.

Abdo, Emily E↗
DOE OSTI2019

Solvent Hold Tank Sample Results for MCU-19-2-3-4 (January 2019), MCU-19-83-84-85 (February 2019), MCU-19-208-209-210 (March 2019) and MCU-19-138-139-140 (March special trim): Quarterly Report

A trend summary of three sets of Solvent Hold Tank (SHT) monthly samples (MCU-19-2-3-4, MCU-19-83-84-85, MCU-19-208-209-210); and a set from a special trim (MCU-19-138-139-140) are reported. Most of the conclusions are based on the March SHT sample (MCU-18-208-209-210). Analyses of the March SHT sample (MCU-19-208-209-210) indicated that the Modifier (Cs-7SB) and the Extractant (MaxCalix) concentrations were below their nominal recommended concentrations (169,000 mg/L and 46,900 mg/L, respectively) by 3% and 6%, respectively. The Suppressor (N,N’,N”–tris(3,7-dimethyloctyl)guanidine or TiDG) concentration has increased since the January 2019 measurement to 1141 mg/L, which is above the minimum recommended concentration (479 mg/L). These new concentrations are consistent with the concentrations observed when MCU was fully operational in 2016. The Semi-Volatile Organic Analysis (SVOA) did not detect any impurities. However, the Fourier Transform Hydrogen Nuclear Magnetic Resonance (FT-HNMR) analysis detected presence of phthalates at a few ppm. The impurity concentration was highest in the January sample and consistently detected in the February and March samples (but always registered as a few ppm or less). Another impurity observed in the samples was mercury. Based on the March SHT sample, up to 25 ± 5 micrograms of mercury per mL of solvent was detected (as the average of the Direct Mercury Analysis (DMA) and X-Ray Fluorescence (XRF) methods). The higher mercury concentration in the solvent (as determined in the last three-monthly samples) is possibly due to the higher mercury concentration in Salt Batches 9 and 10. The gamma concentration (~2.55E5 dpm/mL) measured in the March 2019 SHT samples was consistent with previous values observed when MCU was operating continuously (for example, between December 2016 and January 2017). Statistical analysis of the different analytical methods detected a bias (a statistical difference at 5% level) between the FT-HNMR and HPLC methods when measuring the MaxCalix and Modifier concentration; the FT-HNMR gave a higher concentration possibly due to peak overlapping in the measured data. A bias was also detected when measuring total mercury by the DMA method versus the XRF method with the XRF method reported higher mercury concentrations. The laboratory will continue to monitor the quality of the solvent for any new impurities or degradation of the solvent components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Literature Review on the Impact of Thermolytic Hydrogen Generation Rate from the Next Generation Solvent

A literature review was undertaken to assess the thermolytic hydrogen generation potential of the Next Generation Solvent (NGS) system, which is planned to replace the Original Caustic-Side Solvent Extraction (CSSX) Solvent at the Salt Waste Processing Facility. NGS uses a new extractant and suppressor and the same modifier and organic carrier solvent as the Original CSSX Solvent at different concentrations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

A Review of the Literature on the Radiolytic Stability of the Next-Generation Solvent

The Original Caustic-Side Solvent Extraction (CSSX) solvent (based on the BOBCalixC6 extractant) currently in use at the Salt Waste Processing Facility (SWPF) is set to be replaced by the Next-Generation Solvent (NGS, based on the MaxCalix extractant). Current SWPF flammability safety controls use G-values for volatile gases obtained from radiolysis studies with the Original CSSX solvent. A review of past irradiation tests of both solvent systems was performed to assess the radiolytic stability of NGS with respect to flammable gas generation from radiolysis.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

High Throughput Solvent-free Manufacturing of Battery Electrodes

The project goal is to develop and demonstrate an advanced solvent-free lithium-ion battery electrode process through proposed Advanced Dry Electrode Process (ADEP) equipment, which is expected to exhibit a better binder fibrillization and high throughput and suitable for high performance electrode manufacturing, and commonize the anode and cathode dry processing equipment, supply chain and operation for lithium-ion battery OEMs for replacing the solvent-based slurry casting. Our proposed approach will facilitate low-cost battery production by addressing the following gaps in present dry electrode processing: • Extend the dry electrode fabrication process to lithium-ion battery anode manufacturing • Increase the active material content for anodes and cathodes • Intensify the process through improved mixing, powder rheology and surface modifications • Enable processing of next-generation electrode materials that are not stable to solvent or ambient air exposure. The project objectives include the development of anode-compatible binder and binder fibrillization promoter for low irreversible capacity loss, low electrode binder content yet higher film mechanical strength, and the optimization of solvent-free anode and cathode process for low cost (>60% electrode cost reduction), high performance (10% increase in energy density without sacrificing cycle life) and high throughput to enable next generation lithium-ion battery electrode production. Solvent-free electrode manufacturing will also enable next-generation cell designs based on prelithiated anodes or solid-state electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2026

Calculation of monomer yields, verification of PG concentration approximation, catalyst comparison for neat aromatic RCF, SEM micrographs for postreaction pulps, yields of aqueous-phase sugar derivatives after PG-H2O RCF, reactor pressure transients, GPC comparing pre- and postreaction organic solvent composition, PG-H2O miscibility testing, GPC probing dimer/oligomer fractionation in PG-H2O mixtures for

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

biorefining↗
DOE OSTI2022

Solvent-Induced Selectivity of Isoprene From Bio-Derived Prenol

In this work we demonstrate the selective catalytic conversion of prenol, which is an allylic alcohol that can be prepared from renewable resources to isoprene. The catalyst is an inexpensive molybdenum complex (Molyvan L) designed and used as an additive for lubricants. Isoprene is generated under relatively mild reaction parameters at 130–150°C, for 2 h, under vapor pressure conditions that do not exceed 50 psi. Two cases were studied: one in which Molyvan L was dissolved in a base oil at 1% concentration (weight/weight) and then mixed with a solvent and prenol and the other in which neat Molyvan L was introduced in the reaction and the base oil was replaced with the solvent and prenol. We investigated the selectivity of the reaction using the following solvents in both cases: dodecane, dodecanol, isododecane, octane, blendstock for oxygenate blending (BOB3), a fuel surrogate, a polyalphaolefin (PAO4), and methoxy polyethylene glycol (methoxy PEG350). Although conversion of prenol was above 94% in all experiments, isoprene was formed with various degrees of efficiency alongside a prenol isomeric alcohol, diprenyl ether and mixed ether via intramolecular and intermolecular dehydration reactions. Dodecane appeared to have the highest level of selectivity initially in base oil so we studied the effect of various dodecane-like solvents on isoprene yield and product profile. Surprisingly, octane (similar to dodecane) and isododecane (branched alkane) generated insignificant amounts of byproducts, essentially providing the highly desired isoprene with a very high selectivity. Branching of the solvent does not appear to have an effect on selectivity. Another advantage of this catalyst is the low loadings required to effect the transformation; that is, 0.25% (weight/volume) in the cases using neat Molyvan L and 0.5% (weight/volume) in the cases using Molyvan L dissolved in the base oil. Provided that prenol can be produced in large scale from bioresources, this work would enable the sustainable production of isoprene, in good yield, and with very high selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Diffusion in mixed solvents - On the viscosity question

Linear plots of reaction rate vs reciprocal of solvent viscosity are generally used as the classifying criteria for diffusion controlled reactions in fluid solutions and to determine reaction mechanisms in mixed hydroxylic solvents like glycerol and water. This paper presents data which shows that the above-mentioned criteria are insufficient in many cases where nonideal mixed solvent systems are used to increase solvent viscosity. Data correlations suggest that the excess functions determine the variation in reaction rate constants. Kinetic parameters are presented for sucrose-water and methanol-water solvent systems for a reaction involving Fe(CN)6 and zinc uroporphyrin.

Carapellucci, P. A.↗
NASA NTRS1984

Thermoplastic composite matrices with improved solvent resistance

In order to improve solvent resistance of aromatic thermoplastic polymers, ethynyl-terminated aromatic sulfone polymers (ETS), sulfone/ester polymers (SEPE) containing pendent ethynyl groups, and phenoxy resin containing pendent ethynyl groups are synthesized. Cured polysulfones and phenoxy resins containing ethynyl groups on the ends or pendent on the molecules exhibited systematic behavior in solvent resistance, film flexibility, and toughness as a function of crosslink density. The film and composite properties of a cured solvent-resistant ETS were better than those of a commercially available solvent sensitive polysulfone. The study was part of a NASA program to better understand the trade-offs between solvent resistance, processability and mechanical properties which may be useful in designing composite structures for aerospace vehicles.

Hergenrother, P. M.↗