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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

Manufacturing of thick composite electrode using solvent mixtures

A method of making an electrode includes the step of dispersing an active electrode material and a conductive additive in a solvent to create a mixed dispersion. The solvent has a surface tension less than 40 mN/m and an ozone forming potential of no more than 1.5 lbs. ozone/lb. solvent. A surface of a current collector is treated to raise the surface energy of the surface to at least the surface tension of the solvent or the mixed dispersion. The dispersed active electrode material and conductive additive are deposited on the current collector. The coated surface is heated to remove solvent from the coating.

25 ENERGY STORAGE↗
DOE OSTI2022

Transfer hydrogenation of heavy hydrocarbons with hydrogen-donor solvents

Processes for treating highly viscous hydrocarbons, such as bitumen from oil sands or petroleum residues, with hydrogen-donor solvents are described. The hydrogen-donor solvent is prepared. A mixture of the hydrocarbon and the hydrogen-donor solvent is heated, and the product is cooled to produce a low viscosity and mildly upgraded hydrocarbon. The hydrogen-donor solvent can be modified to improve its solvent usefulness.

Chauhan, Satya P.↗
DOE OSTI2019

Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts

Liquid phase, reductive deoxygenation of biomass derived platform chemicals over transition metal surfaces constitutes an efficient scheme for upgrading lignocellulosic biomass. The solvation effects on the reaction kinetics of the hydrodeoxygenation (HDO) of levulinic acid (LA) towards the formation of γ-valerolactone (GVL) over Ru(0001) has been studied in three condensed phase media, i.e., liquid water, methanol, and 1,4-dioxane. Detailed microkinetic models have been developed incorporating various catalytic pathways including formation of 4-hydroxypentanoic acid (HPA) and α-angelicalactone (AGL) to simulate the catalytic activity of Ru(0001) under various reaction conditions of solvent, temperature, and partial pressures. Our microkinetic models suggest that direct catalytic conversion with alkoxy formation is the preferred reaction mechanism in all reaction environments. Here, we find that water facilitates the reaction kinetics significantly and that the solvent effect is strongest at lower temperatures (T<373 K). Here, rate increases due to liquid water solvation effects of 2-4 orders of magnitude are observed. All solvents increase the rate of reaction relative to the gas phase; however, solvation effects decrease with decrease in polarity. 1,4-dioxane increases the rate only minimally due to competitive adsorption of the solvent molecules despite facilitating the partially rate controlling step of the LA hydrogenation to an alkoxy intermediate.

1,4-Dioxane↗
DOE OSTI2023

Ten-Fold Solvent Kinetic Isotope Effect for the Nonradiative Relaxation of the Aqueous Ferrate(VI) Ion

Hypervalent iron intermediates have been invoked in the catalytic cycles of many metalloproteins, and thus, it is crucial to understand how the coupling between such species and their environment can impact their chemical and physical properties in such contexts. In this work, we take advantage of the solvent kinetic isotope effect (SKIE) to gain insight into the nonradiative deactivation of electronic excited states of the aqueous ferrate-(VI) ion. Here we observe an exceptionally large SKIE of 9.7 for the nanosecond-scale relaxation of the lowest energy triplet ligand field state to the ground state. Proton inventory studies demonstrate that a single solvent O-H bond is coupled to the ion during deactivation, likely due to the sparse vibrational structure of ferrate-(VI). Such a mechanism is consistent with that reported for the deactivation of f-f excited states of aqueous trivalent lanthanides, which exhibit comparably large SKIE values. This phenomenon is ascribed entirely to dissipation of energy into a higher overtone of a solvent acceptor mode, as any impact on the apparent relaxation rate due to a change in solvent viscosity is negligible.

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

Tuning the Solvation and Solubility Properties of Molecularly Heterogeneous Nonionic Deep Eutectic Solvents via Interface Organization

Common separation techniques, such as liquid− liquid extraction, are usually used for extractions and purifications due to their industrial scalability and affordability. However, these well-established practices are hindered by low selectivity and challenges in recovering solutes and solvents. Deep eutectic solvents (DES), a fairly new type of solvent, have the potential to overcome these issues. DESs are binary mixtures whose physical properties can be tuned by selecting the appropriate precursors to facilitate and/or enhance processes such as extraction. A promising DES for selective separations is formed when lauric acid (LA) is mixed with N-methylacetamide (NMA). This LA-NMA DES has a heterogeneous microscopic structure that can solvate compounds with completely different polarities. This study explores how forming an organized structure on the mesoscale affects the solubility of nonpolar solutes in nonionic DESs. To this end, the molecular and mesoscale structures and their effect on the solubility and solvation properties are evaluated for the LA-NMA DES and two new DESs with slight chemical variations in their precursors. It is observed that the organization of the nonpolar DES domains and, consequently, of their interfaces directly relates to the solubility of nonpolar compounds. Specifically, correctly selecting the DES precursors that form organized nonpolar domains leads to an organized interface in which the nonpolar solutes are solvated, thereby increasing the solubility. Additionally, enhanced dissolution power was observed in a completely different DES with mesoscale order in its molecular structure and composed of menthol and lauric acid. The latter result further validates the proposed tunability of the DES dissolution power through organized interfaces, extending it beyond a specific DES family and opening the possibility of new extraction-tailored designer solvents.

Extraction↗
DOE OSTI2023

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Biphasic dehydration of fructose to 5-hydroxymethylfurfural (HMF) has shown unprecedented increases in productivity, but a mechanistic understanding is lacking. Herein, we couple fast experimental reaction kinetics, multiscale modeling (phase behavior, classical molecular dynamics(MD), and quantum mechanics/molecular mechanics MD), in situ sampling, and IR and 13 C-NMR spectroscopy to elucidate the complex effects of nonpolar extracting organic solvents on the kinetics of fructose dehydration. We show that these organic solvents can reach significant mutual solubility with water at reaction temperatures, enabling the partition of the sugar and catalyst into the extracting phase. In the organic-rich environment, the dehydration of fructose proceeds faster and more selectively than in water due to increased relative abundance of the reactive furanose isomer, enhanced water–catalyst–substrate interactions driven by nanophase separation, and higher product stability stemming from preferential solvation. Furthermore, we demonstrate that these solvent effects impact other critical biphasic reactions in biomass upgrading and provide qualitative principles for solvent selection.

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

Investigating the Role π -Rich Solvents Play in the Growth of Cesium Lead Bromide Nanocrystals

In this report, the role that a high-boiling-point solvent type plays on the nucleation and growth, morphology, and crystal-phase transformation of cesium lead bromide nanocrystals (CsPbBr 3 ) is studied. The CsPbBr 3 products were compared between a one-pot growth mechanism at room temperature (RT) versus a hot-injection mechanism (HI) control using dibenzyl ether (DBE), diphenyl ether (DPE), dioctyl ether (DOE), or 1- octadecene (ODE). The coordination between these solvents and the PbBr 2 salt precursors resulted in different plumbate [PbSBr n ] 2−n precursors being formed. The S-to-Pb 2+ coordination within [PbSBr n ] 2−n was probed by UV−vis and solvent-phase 207 Pb NMR, both of which showed considerable coordination between [PbSBr n ] 2−n and the π-rich DBE and DPE, whose reactivity affected CsPbBr 3 growth. The effect was more pronounced for CsPbBr 3 prepared via RT, where the morphology was tunable, with π-rich solvents producing thin rod-like CsPbB r3 with a blue emission, compared to the green-emitting thicker platelets formed via HI. While XRD showed crystalline products for both RT and HI, with orthorhombic and cubic forms, respectively, the RT products had considerable surface defects, as was indicated by lower quantum yields, and to understand this the photoluminescent lifetimes were measured by time-correlated single photon counting.

207Pb NMR↗
DOE OSTI2025

Mechanisms and Energetics of CO 2 Chemisorption in Choline-Based Eutectic Solvents

Understanding the influences of proton sharing and hydrogen transfer in amine and hydroxyl functionalized eutectic solvents is important for tuning CO 2 binding as they relate to the chemisorption capacity and energetics of solvent regeneration in carbon capture. In this study, we examine how the CO 2 binding mechanism and energetics vary in eutectic solvents composed of choline-based hydrogen-bond acceptors (HBAs) with amine and hydroxyl moieties and ethylene glycol (EG), propylene glycol (PG), 1,2-butanediol (BD), and monoethanolamine (MEA)-type hydrogen-bond donors (HBDs), through absorption–desorption experiments and spectral analysis, supported with density functional theory (DFT) calculations. While the HBD-CO 2 complex is the major and the thermodynamically more favored product of absorption in all of the examined eutectic solvents, this complexation is only possible proceeding a proton transfer from HBD to the HBA in diol-based systems (EG, PG, BD). The interplay between HBA-CO 2 and HBD-CO 2 speciation is governed by the HBD concentration, basicity, and steric effects, with increased HBD-CO 2 interactions in the presence of smaller HBDs (size: BD > PG > EG). On the other hand, in MEA-based systems, CO 2 readily binds to the amine followed by a proton transfer from the amine to the HBA as confirmed by DFT calculations. In this way, the MEA-CO 2 chemisorption capacities exceeded that of the conventional amine (up to 0.93 mol of CO 2 per mol of MEA versus 0.5). Furthermore, the increase in CO 2 capacities and enhanced binding in eutectics including MEA or the more basic HBAs also resulted in regeneration temperatures of 70 to 60 °C with calculated reaction energies of −82 to −57 kJ/mol, compared to 50 °C for others with weaker binding, following CO 2 absorption at 25 °C.

absorption↗
DOE OSTI2020

Environmental, Health and Safety Assessment Application of a Heat Integrated, Post-combustion CO2 Capture System Using Monoethanolamine and Hitachi H3-1 Solvent at the E.W. Brown Coal-fired Power Plant

An Environmental Health and Safety (EH&S) Assessment was completed for operation of a pilot scale carbon dioxide (CO2) capture system (CCS) at the Louisville Gas & Electric (LG&E) and Kentucky Utilities (KU) Energy, LLC (LG&E-KU) E. W. Brown Generating Station in Harrodsburg, Mercer County, Kentucky. The pilot system was evaluated using two CO2 capture solvents, monoethanolamine (MEA) and Hitachi’s H3-1 solvent. The purpose of the EH&S Assessment was to determine if there were any unacceptable environmental, health or safety concerns that may prevent operation or environmental permitting of a larger scale pilot scale plant. The assessment included review of process flow diagrams, input and output flow rates for primary materials, literature describing similar processes and chemicals used or created during the process, actual air emission and wastewater test data and air emission calculations. The evaluation included identification of risks related to hazardous chemicals, air emissions, wastewater discharges, solid wastes generated and employee hazards. Most potential EH&S issues that were identified are commonly found and successfully managed at large industrial facilities. No risks were identified that could not be successfully managed or would likely prevent implementation or environmental permitting of the pilot or larger scale plant. Potential exposures and resulting health risks from exposure to low concentrations of nitrosamines generated from degradation of the Hitachi H3-1 and possibly MEA solvents may be a health concern for site workers, but additional investigation is needed to accurately assess this risk. Applying the information gained from operating the pilot plant, performing air emission testing and used solvent testing to a large-scale facility at a commercial coal-fired electric generating plant suggests additional air emission control measures may be necessary to reduce potential site worker health risks and possibly community risks. Depending upon the location and regional air quality, considerable effort may be required to obtain the necessary air permit for construction and operation of a similarly configured large-scale PCCCS facility.

gas separation↗
DOE OSTI2020

Environmental, Health and Safety Assessment Application of a Heat Integrated, Post-combustion CO 2 Capture System Using Monoethanolamine and Hitachi H3-1 Solvent at the E.W. Brown Coal-Fired Power Plant

An Environmental Health and Safety (EH&S) Assessment was completed for operation of a pilot scale carbon dioxide (CO 2 ) capture system (CCS) at the Louisville Gas & Electric (LG&E) and Kentucky Utilities (KU) Energy, LLC (LG&E-KU) E. W. Brown Generating Station in Harrodsburg, Mercer County, Kentucky. The pilot system was evaluated using two CO 2 capture solvents, monoethanolamine (MEA) and Hitachi’s H3-1 solvent. The purpose of the EH&S Assessment was to determine if there were any unacceptable environmental, health or safety concerns that may prevent operation or environmental permitting of a larger scale pilot scale plant. The assessment included review of process flow diagrams, input and output flow rates for primary materials, literature describing similar processes and chemicals used or created during the process, actual air emission and wastewater test data and air emission calculations. The evaluation included identification of risks related to hazardous chemicals, air emissions, wastewater discharges, solid wastes generated and employee hazards. Most potential EH&S issues that were identified are commonly found and successfully managed at large industrial facilities. No risks were identified that could not be successfully managed or would likely prevent implementation or environmental permitting of the pilot or larger scale plant. Potential exposures and resulting health risks from exposure to low concentrations of nitrosamines generated from degradation of the Hitachi H3-1 and possibly MEA solvents may be a health concern for site workers, but additional investigation is needed to accurately assess this risk. Applying the information gained from operating the pilot plant, performing air emission testing and used solvent testing to a large-scale facility at a commercial coal-fired electric generating plant suggests additional air emission control measures may be necessary to reduce potential site worker health risks and possibly community risks. Depending upon the location and regional air quality, considerable effort may be required to obtain the necessary air permit for construction and operation of a similarly configured large-scale PCCCS facility.

gas separation↗
DOE OSTI2022

Effect of Aromatic Solvents Residuals on Electron Mobility of Organic Single Crystals

Balanced electron and hole transport properties are essential for various organic electrical/optoelectrical applications such as organic solar cells, complementary circuits, and light-emitting transistors. However, the electron transport in organic semiconductor lags far behind the hole side, making it with vital significance to seek the factors that limit the electron mobility. Here, the authors demonstrate that the π-conjugated solvents, as essential components in the widely-used solution processing techniques, can significantly suppress the electron transport if they are not properly removed and trapped as residuals. Single crystals of typical p-type materials exhibit a transition from p-type behavior to ambipolar conductance via reducing the amount of solvent residuals, and the same effect is confirmed by varied p-type materials and solvents. The highest electron mobility reaches 0.027 cm 2 V –1 s –1 and 0.029 cm 2 V –1 s –1 for 6,13-bis(triisopropylsilylethynyl)pentacene and 5,15-bis(triisopropylsilylethynyl)tetrabenzoporphyrin, respectively. Finally, this work discloses the non-negligible existence of solvent residuals even in high quality, long-range ordered organic single crystals, and further provides efficient strategies to harvest the n-type behaviors of organic semiconductor materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Shear and extensional rheology of polyethylenes recycled using a solvent dissolution process

There is high market demand for increasing the viability of current plastic recycling processes. In this work rheology is used to evaluate the mechanical properties of a solvent dissolution recycled polymer compared to its virgin untreated precursor. Solvent dissolution and precipitation are used to target multi-layer, multi-component, industry films, which cannot be mechanically recycled. Polyethylene was chosen as the primary polymer of interest. Polymer thermal stability was monitored via time-resolved rheology; consecutive frequency sweeps over the course of an hour while under isothermal conditions. Additional rheological experiments were performed within the identified thermally stable conditions. Small-angle oscillatory shear was complemented with steady shear viscosity experiments over a wide range of shear rates. Extensional rheology was used to determine changes in molecular weight and cross link density. As a result, rheological characterization is supplemented with gas chromatography–mass spectrometry of the solvent wash to determine components stripped from the virgin polymers during solvent treatment.

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

Green-Solvent Processed Blade-Coating Organic Solar Cells with an Efficiency Approaching 19% Enabled by Alkyl-Tailored Acceptors

Power-conversion-efficiencies (PCEs) of organic solar cells (OSCs) in laboratory, normally processed by spin-coating technology with toxic halogenated solvents, have reached over 19%. However, there is usually a marked PCE drop when the blade-coating and/or green-solvents toward large-scale printing are used instead, which hampers the practical development of OSCs. Here, a new series of N-alkyl-tailored small molecule acceptors named YR-SeNF with a same molecular main backbone are developed by combining selenium-fused central-core and naphthalene-fused end-group. Thanks to the N-alkyl engineering, NIR-absorbing YR-SeNF series show different crystallinity, packing patterns, and miscibility with polymeric donor. The studies exhibit that the molecular packing, crystallinity, and vertical distribution of active layer morphologies are well optimized by introducing newly designed guest acceptor associated with tailored N-alkyl chains, providing the improved charge transfer dynamics and stability for the PM6:L8-BO:YR-SeNF-based OSCs. As a result, a record-high PCE approaching 19% is achieved in the blade-coating OSCs fabricated from a green-solvent o-xylene with high-boiling point. Notably, ternary OSCs offer robust operating stability under maximum-power-point tracking and well-keep > 80% of the initial PCEs for even over 400 h. Our alkyl-tailored guest acceptor strategy provides a unique approach to develop green-solvent and blade-coating processed high-efficiency and operating stable OSCs, which paves a way for industrial development.

14 SOLAR ENERGY↗
DOE OSTI2021

Encapsulation of highly viscous CO 2 capture solvents for enhanced capture kinetics: Modeling investigation of mass transfer mechanisms

The encapsulation of highly viscous liquid-like Nanoparticle Organic Hybrid Materials (NOHMs) inside a gas permeable polymer to form SIPs (Solvent Impregnated Polymers) significantly enhanced the CO 2 capture kinetics of NOHMs, leading to a remarkable 50-fold increase in CO 2 flux compared to the neat NOHMs. To understand the mechanism for enhanced CO 2 mass transfer within these hybrid materials, kinetic modeling of CO 2 uptake into SIPs containing polyethylenimine functionalized NOHMs, denoted NPEI-SIP, was conducted. CO 2 mass transfer into NPEI-SIP films was found to conform, both qualitatively and quantitatively, with a diffusion-controlled moving front model. The diffusion-controlled model was also used to simulate CO 2 uptake within a fixed bed containing polydisperse NPEI-SIP particles, and this model accurately predicted experimentally measured breakthrough curves at 25 °C and 50 °C. The 50-fold increase in gas flux was shown to be a consequence of the very large CO 2 permeability within the polymer–solvent composite. Furthermore, the increase in gas flux is also dependent on the diffusion–reaction regime in which the chemical solvent operates, and the largest improvement will occur when immobilizing solvents, such as NOHMs, which operate in the instantaneous-reaction regime. The CO 2 capacity (~3 mol CO 2 /kg) and saturation time (~5 min) of 430 μm SIP particles were comparable to popular CO 2 chemisorption materials such as amine grafted silicates, in spite of the slow kinetics of NOHM-I-PEI in liquid form (CO 2 saturation time ~24 h for a 1 mm thin film).

36 MATERIALS SCIENCE↗
DOE OSTI2021

Modeling swelling behavior of hydrogels in aqueous organic solvents

Hydrogel, a three-dimensional elastic structure of cross-linked polymer chains, swells or deswells when immersed in aqueous organic solutions. The swelling of hydrogels depends on temperature, solvent composition, and hydrogel structure as the thermodynamic driving forces for hydrogel swelling are due to solvent – hydrogel interactions and expansion of elastic network. Here in this work, polymer Nonrandom Two-Liquid activity coefficient model is used to account for the solvent – hydrogel interactions and a semi-empirical expression for rubber elasticity is used to describe the expansion of elastic network. The model successfully correlates data for both swelling and equilibrium phase compositions for n-isopropyl acrylamide hydrogels in water – ethanol, water – acetone, water – n-butanol, and water – methyl isobutyl ketone mixed solvents.

42 ENGINEERING↗
DOE OSTI2020

Deep eutectic solvents in separations: Methods of preparation, polarity, and applications in extractions and capillary electrochromatography

Deep eutectic solvents (DESs) have emerged as alternatives to conventional organic solvents and ionic liquids (ILs). Their tunable and designer physio-chemical properties, low cost, and ease of preparation make them attractive solvent systems for use in extractions and additives to chromatographic separations. However, due to the diverse range of hydrogen bond acceptors and donors that comprise DESs, choosing the appropriate solvent for separations can be challenging. This work discusses all methods of DES preparation and details their advantages and disadvantages. Since polarity is an important aspect in their use in separations, the classification of DESs based on the betaine dye and nile red scales as well as Kamlet-Taft parameters is also discussed. Finally, a summary of applications of DESs in various extraction processes (phenolics, fuels, metals, proteins, carbohydrates), solid-phase extraction, solid-phase microextraction, as well as capillary electrochromatography is provided.

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

Analysis of persistent contaminants and personal care products by dispersive liquid-liquid microextraction using hydrophobic magnetic deep eutectic solvents

Here, in this work, hydrophobic magnetic deep eutectic solvents (HMDESs) were used in the development of a simple and rapid dispersive liquid-liquid microextraction (DLLME) approach coupled to high performance liquid chromatography with UV detection (HPLC-UV) for the determination of ten organic contaminants including five polycyclic aromatic hydrocarbons, four UV filters, and a pesticide from water at trace levels. The HMDESs were prepared by mixing a hydrogen bond acceptor, metal halide salt, and hydrogen bond donor in suitable molar ratios. Two HMDESs, 2 tetraoctylammonium bromide ([N 8888 + ][Br - ]): cobalt chloride (CoCl 2 ): 4 octanoic acid (OA) and 3 trioctylphosphine oxide (TOPO): neodymium chloride (NdCl 3 ): 3 OA, offered the highest analyte extraction efficiency overall and were chosen as suitable solvents for validation of the microextraction method. Under optimized extraction conditions, the method required 30 µL of HMDES as extraction solvent, acetone (87.5 µL) as disperser solvent, a NaCl concentration of 30% (w/v), and an extraction time of 120 s at 20°C. Enrichment factors of the analytes ranged from 44.6 for 3-(4-methylbenzylindene) camphor to 66.0 for 2-ethylhexyl-4-(dimethyl)aminobenzoate. The method provided low limits of detection (LODs) ranging from 0.5 to 4.5 µg L -1 , and acceptable precision, with RSD values lower than 9.6%. Furthermore, the validated method was successfully applied for tap and lake water analysis, resulting in relative recoveries of spiked samples ranging between 94.7 and 119.2%.

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

A fast computational framework for the design of solvent-based plastic recycling processes

Multicomponent plastics cannot be processed using mechanical recycling technologies, hindering efforts to deal with plastic waste. Multicomponent plastics include multilayer plastic films, which are widely used for food and healthcare packaging. Multilayer films combine several layers (potentially dozens) of different polymers to protect products from external factors (e.g., oxygen, water, temperature, shock, and light). Solvent-based separation processes have emerged as a promising alternative to recycle these complex materials. For instance, the Solvent-Targeted Recovery and Precipitation (STRAP TM ) process uses sequential solvent washes to selectively dissolve and separate constituent polymers from multicomponent plastic waste, including films. STRAP TM process design (separation sequence, type of solvents, and operating conditions) changes significantly depending on the design of the multilayer plastic film (e.g., number, types, and proportions of polymers). The ability to quickly quantify the economic and environmental benefits of diverse STRAP TM process designs is essential to accelerate the development of sustainable recycling processes and more recyclable multilayer film products. In this work, we present a fast computational framework that integrates molecular-scale models, process modeling, and techno-economic and life cycle analysis to quickly evaluate STRAP TM designs. The computational framework is general and can be used to study the processing of complex multilayer plastic waste streams that contain many layers. Furthermore, we highlight the different uses of the framework via targeted case studies.

Computational framework↗