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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The physical basis for solvent flow in organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is an emerging membrane technology that could revolutionize chemical separations in numerous vital industries. Despite its significance, there remains a lack of fundamental understanding of solvent transport mechanisms in OSN membranes. Here, we use an extended Flory-Rehner theory, nonequilibrium molecular dynamic simulations, and organic solvent transport experiments to demonstrate that solvent flow in OSN membranes is driven by a pressure gradient. We show that solvent molecules migrate as clusters through interconnected pathways within the membrane pore structure, challenging the widely accepted diffusion-based view of solvent transport in OSN. We further reveal that solvent permeance is dependent on solvent affinity to the OSN membrane, which, in turn, controls the membrane pore structure. Our fundamental insights lay the scientific groundwork for the development of next-generation OSN membranes.

42 ENGINEERING↗
DOE OSTI2019

Capture and release of acid gasses using tunable organic solvents with binding organic liquids

A class of water lean, organic solvents that can bind with various acid gasses to form acid gas bound molecules having a high degree of intramolecular hydrogen bonding which enables their use as regenerable solvents for acid gas capture. Unlike the other devices described in the prior art, the present invention takes advantage of shortened distances between the portions of the molecule that form hydrogen bonds within the structures when loaded with an acid gas so as to create a molecule with a higher internal bonding affinity and a reduced proclivity for agglomeration with other molecules.

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

Ion Solvation-Driven Liquid–Liquid Phase Separation in Divalent Electrolytes with Miscible Organic Solvents

Liquid–liquid phase separation (LLPS) is a common phenomenon, but LLPS of electrolytes prepared in miscible organic solvents is rarely documented. Here we report four cases of LLPS that occur in MgTFSI 2 or ZnTFSI 2 electrolytes in mixed organic solvents. The conditions for the formation of this LLPS share four common features: cations with high charge density; bulky anions with low charge density; a strongly coordinating solvent with high compressibility; and a relatively weak coordinating solvent with low relative permittivity and high mobility. With these conditions, the cations tend to draw the strongly coordinating solvents together to form a densely-packed, energetically-favorable ion solvation region, while the cosolvents with low relative permittivity tend to repel ions to form an ion-depleted dilute phase. Furthermore, in the dilute upper layer with more than 300 solvent molecules per cation, ion pairs and large ion aggregates are clearly evidenced, due to the incomplete screening of electrostatic interactions by the weaker cosolvent. This LLPS driven by ion solvation may be more common in multivalent electrolytes and is a design consideration with mixed solvents that should not be overlooked.

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

Mechanistic study of pH effect on organic solvent nanofiltration using carboxylated covalent organic framework as a modeling and experimental platform

Covalent organic framework (COF) membranes for organic solvent nanofiltration (OSN) have attracted growing interest due to their high stability, well-defined pore size, and controllable pore functionality. In aqueous nanofiltration processes, solution pH has a significant effect on membrane permeability, selectivity, and fouling. However, our understanding of pH effects on OSN processes is still limited. In this work, we present experimental and reactive force field molecular dynamics (ReaxFF MD) simulation results on the effect of pH on OSN using a well-characterized carboxylated COF (C-COF) membrane. Filtration experimental and modeling results both demonstrate that pH changes can affect solvent permeance and solute rejection dramatically. Specifically, methanol permeance decreases with the increase of NaOH and HCl concentration, respectively. When Alcian Blue dye was used as the solute in methanol, the selectivity increased from 23% to 98% when changing the feed pH from 2.2 to 10.1, respectively. While ReaxFF MD results show that C-COF solvated pore size is only marginally affected by the pH of solution, methanol diffusion is affected by the size of methanol-solvated Na + and Cl - ions, which increase with increasing Na + and Cl - concentrations. Solution pH change also affected solute solvation layer thicknesses and C-COF pore charges, contributing to the significant AB dye selectivity increase with pH increase. To summarize, we have shown that dramatic changes in C-COF selectivity are not anomalous in OSN, but are instead controllable by varying feed solution pH to modify solvated solute radii and surface charge.

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

Screening of metal complexes and organic solvents using the COSMOSAC-LANL model to enhance the energy density in a non-aqueous redox flow cell: an insight into the solubility

In this paper, we have proposed a first-principles methodology to screen transition metal complexes against a particular organic solvent and organic solvents against a particular transition metal complex based on their solubility information without the knowledge of heat of fusion and melting temperature. The energy density of a non-aqueous redox flow cell directly depends on the solubility of the redox active species in the non-aqueous medium. Here, we have used the “COSMOSAC-LANL” activity coefficient model which is based on first-principles COSMO calculations where the microscopic information is passed to the macroscopic world via a dielectric continuum solvation model, followed by a post-statistical thermodynamic treatment of the self-consistent properties of the solute particle to calculate the solubility. To model the activity coefficient at infinite dilution for the binary mixtures, a 3-suffix Margules (3sM) function is introduced for the quantitative estimation of the asymmetric interactions and, for the combinatorial term, the Staverman–Guggenheim (SG) form is used. The new activity coefficient model is separately called the “LANL” activity coefficient model. The metal complex and the organic solvent have been treated as a simple binary mixture. The present model has been applied to a set of 14 different organic solvents and 16 different transition metal complexes. Using the new LANL activity coefficient model in combination with the ADF-COSMOSAC-2013 model, we have shown how one can improve the solubility of a transition metal complex in an organic solvent. We applied our model to screen 84 binary mixtures to predict the compatible pair of redox active species and organic solvent to increase the energy density. The solvation mechanism of the transition metal complexes in the organic solvents was obtained using the new model. The results have been compared with the experimental and theoretical results where they are available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Scalable and adaptable two-ligand co-solvent transfer methodology for gold bipyramids to organic solvents

Large and faceted nanoparticles, such as gold bipyramids, presently require synthesis using alkyl ammonium halide ligands in aqueous conditions to stabilize the structure, which impedes subsequent transfer and suspension of such nanoparticles in low polarity solvents despite success with few nanometer gold nanoparticles of shapes such as spheres. Phase transfer methodologies present a feasible avenue to maintain colloidal stability of suspensions and move high surface energy particles into organic solvent environments. Here, we present a method to yield stable suspensions of gold bipyramids in low-polarity solvents, including methanol, dimethylformamide, chloroform, and toluene, through the requisite combination of two capping agents and the presence of a co-solvent. By utilizing PEG-SH functionalization for stability, dodecanethiol (DDT) as the organic-soluble capping agent, and methanol to aid in the phase transfer, gold bipyramids with a wide-range of aspect ratios and sizes can be transferred between water and chloroform readily and maintain colloidal stability. Subsequent transfer to various organic and low-polarity solvents is then demonstrated for the first time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1978

Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

Fielder, W. L.↗
DOE OSTI2018

High solvent-resistant and integrally crosslinked polyimide-based composite membranes for organic solvent nanofiltration

This study reports a new class of integral polyimide (PI)-based thin film composite (TFC) membranes (with improved solvent resistance in both the skin layer and the substrate) for organic solvent nanofiltration (OSN). The OSN membrane was prepared via interfacial polymerization (IP) onto a PI ultrafiltration (UF) substrate, followed by an imidization, a chemical crosslinking, and a solvent activation process. During the IP process, m-phenylenediamine (MPD), dopamine (DA), and 1,2,4,5-benzene tetracarboxylic acyl chloride (BTAC) were respectively used as an aqueous monomer, an aqueous additive, and an organic monomer. We proved that amide bonding formed between MPD and the PI substrate during the immersion of the substrate in the aqueous MPD solution, thus providing a strong binding between the substrate and the subsequently formed skin layer of polyamide acid (PAA), which was formed due to reaction between MPD and BTAC during the IP process. DA contains amine group and could also help build a strong binding between the substrate and the skin layer during the same IP process. The subsequent imidization step converted the PAA molecules of the skin layer into PI polymers, which was quite similar to that of the substrate. The final crosslinking step crosslinked not only the inner molecules of the skin layer, and the inner molecules of the substrate, but also the interface molecules between the skin and substrate so as to form an integral composite membrane with improving solvent resistance. Finally, the fabricated OSN membranes under optimal preparation conditions exhibited an ethanol permeance of 2.03 L m -2 h -1 bar -1 with a rejection of 98% for Rhodamine B (479 Da) and exhibited an outstanding organic solvent resistance without compromising separation performance during the persistent immersion in DMF at 80 °C for two weeks, indicating a promising prospective in OSN applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Correlating Interlayer Spacing and Separation Capability of Graphene Oxide Membranes in Organic Solvents

Membranes synthesized by stacking two-dimensional graphene oxide (GO) hold great promise for applications in organic solvent nanofiltration. However, the performance of a layer-stacked GO membrane in organic solvent nanofiltration can be significantly affected by its swelling and interlayer spacing, which have not been systematically characterized. In this study, the interlayer spacing of the layer-stacked GO membrane in different organic solvents was experimentally characterized by liquid-phase ellipsometry. To understand the swelling mechanism, the solubility parameters of GO were experimentally determined and used to mathematically predict the Hansen solubility distance between GO and solvents, which is found to be a good predictor for GO swelling and interlayer spacing. Solvents with a small solubility distance (e.g., dimethylformamide, N-methyl-2-pyrrolidone) tend to cause significant GO swelling, resulting in an interlayer spacing of up to 2.7 nm. Solvents with a solubility distance larger than 9.5 (e.g., ethanol, acetone, hexane, and toluene) only cause minor swelling and are thus able to maintain an interlayer spacing of around 1 nm. Correspondingly, GO membranes in solvents with a large solubility distance exhibit good separation performance, for example, rejection of more than 90% of the small organic dye molecules (e.g., rhodamine B and methylene blue) in ethanol and acetone. Additionally, solvents with a large solubility distance result in a high slip velocity in GO channels and thus high solvent flux through the GO membrane. Finally, the GO membrane performs better in solvents that are unlike GO, i.e., solvents with large solubility distance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Smart, Marshall C.↗
DOE OSTI2017

Extraction of 211 At from nitric acid solutions into various organic solvents for use as an α-source for radiation chemistry studies

The partitioning of 211 At from an irradiated bismuth target using solvent extraction into several organic solvents is presented. Although astatine speciation is difficult to measure given its invariably low chemical concentration its extraction here is consistent with the existence of a cationic species in nitric acid that is not reduced upon contact with the organic phase. This is consistent with previous work that postulated the most probable species in acidic solution as AtO + . The technique presented here has a simple experimental set up and provides high specific activity astatine solutions compatible for use in α-radiolysis studies.

07 ISOTOPE AND RADIATION SOURCES↗
NASA NTRS2011

Dispersion and separation of nanostructured carbon in organic solvents

The present invention relates to dispersions of nanostructured carbon in organic solvents containing alkyl amide compounds and/or diamide compounds. The invention also relates to methods of dispersing nanostructured carbon in organic solvents and methods of mobilizing nanostructured carbon. Also disclosed are methods of determining the purity of nanostructured carbon.

Landi, Brian J.↗
NASA NTRS2011

Dispersion and separation of nanostructured carbon in organic solvents

The present invention relates to dispersions of nanostructured carbon in organic solvents containing alkyl amide compounds and/or diamide compounds. The invention also relates to methods of dispersing nanostructured carbon in organic solvents and methods of mobilizing nanostructured carbon. Also disclosed are methods of determining the purity of nanostructured carbon.

Landi, Brian J.↗