Search NASA⌕ Search

SEARCH · Search NASA

Results for “Ionic Solutions”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS2023

Multiphysics Modeling of Electrode Dissolution under Hydrodynamic Conditions in Low Conductivity Water

Efficient plug-flow electrochemical reactors are characterized by their ability to effectively convert species with significant ionic strength and/or with the assistance of a well-behaved electrolyte. Because of the classic electroconductivity requirement, electrochemical reactors are not particularly attractive options for applications with low-conductivity conditions, especially for low-pressure feeds. However, these reactors can still find application in dedicated processes such as ultra-clean water conditioning and biological-coupled separation systems. Consequently, a multi-physics model was developed using COMSOL Multiphysics to characterize different reactor-design conditions based on the Tertiary Current Distribution which accounts for the effects of expected variations in electrolyte composition and ionic strength on the electrochemical process, as well as solution resistance and electrode kinetics. The modelling framework presented here employs single-phase laminar fluid flow, the Nernst-Planck equation, the water-based electroneutrality condition, and concentration-dependent overpotentials. This investigation particularly explores the electrolysis process of “anodic dissolution,” in which elemental species dissociate from the solid matrix of the electrode and enter the liquid phase of the electrolyte as soluble ions. The reactor configuration of interest has a rectangular parallel-electrode design and is operated galvanostatically. A series of parametric studies are carried out to inspect the response of the system when hydrodynamic, kinetic, and geometric conditions are changed. The parametric sweep resulted in variable effluent concentrations and system voltage, which reveal underlaying optimization patterns for electrode dissolution in low conductivity water.

Multiphysics↗
DOE OSTI2020

Electrolyte Solvation and Ionic Association. VII. Correlating Raman Spectroscopic Data with Solvate Species

Raman spectroscopy is a widely utilized method for determining information about the solvate species present in electrolyte solutions. Difficulties arise, however, when interpreting the Raman data in terms of correlating the spectroscopic vibrational bands with specific solvate species. Examples are provided to demonstrate how erroneous conclusions may be drawn with regard to the identity and population (distribution) of the solvent-separated ion pair (SSIP), contact ion pair (CIP) and aggregate (AGG) solvate species frequently mentioned in the scientific literature.

contact ion pairs↗
DOE OSTI2022

Polymers in Deep Eutectic Solvents

The project investigated the behavior of polymers in ionic liquids such as deep eutectic solvents using an array of techniques. These included the development of atomistic force fields, coarse graining these force fields to the united atom level, large scale molecular dynamics (MD) simulations using new thermostat algorithms, and machine learning (ML) methods for the phase behavior. The project demonstrated the feasibility and accuracy of first principles force fields for ionic liquids, deep-eutectic solvents, and urea-water mixtures. A novel hierarchical coarse graining method was then used to develop accurate and efficient united-atom models, using which microsecond simulations were performed for polymers in ionic liquids. These simulations were in quantitative agreement with experiment, thus resolving previous controversies. Methods were also developed to obtain the potential of mean force between complex ions in solution. Finally, supervised ML methods were developed for the phase behavior of polymers in ionic liquids.

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

Effect of Ionic Strength and Anion Identity on Rare‐Earth Element Chelation by Poly(acrylic acid)

Abstract Rare‐earth elements (REEs) are critical components of many modern technologies, but their efficient separation and purification continue to pose significant challenges. Metal‐binding polymers may enable the development of promising alternative approaches to conventional separation techniques (e.g., solvent extraction), and insights into the interactions between the metal ions and polymers in solution are crucial to such development. In this work, the effect of ionic strength on the chelation of REEs by poly(acrylic acid) is investigated using isothermal titration calorimetry (ITC) to measure the metal‐binding thermodynamics. ITC experiments revealed that when ionic strength increases from increasing the sodium acetate buffer strength, polymer‐REE binding becomes increasingly disfavored. However, when ionic strength is increased by the addition of sodium chloride, binding again becomes increasingly disfavored, but to a lesser extent than when ionic strength increases from increasing the buffer strength. Additionally, the reduction in binding affinity is enthalpically driven when ionic strength is raised with sodium chloride, while it is entropically driven when raised with sodium acetate buffer, suggesting competive binding by the acetate ions. These results highlight the importance of ionic strength in polymer‐metal binding thermodynamics and will guide the development of new processes for the purification of critical metals.

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

Techno-Economic and Life Cycle Assessment of Chemical Recycling and Upcycling of Mixed Plastics Waste Containing Poly-vinyl-chloride

Developing technologies that completely remove chlorine from plastic waste can allow its chemical recycling and upcycling with catalytic methods. Here, this study compares eight processes involving different dechlorination methods (absorption columns, adsorption in beds of zeolites, catalytic dechlorination, and dissolution in ionic liquids) and chemical conversion technologies (incineration, pyrolysis, hydrogenolysis) to upgrade mixed plastics waste to various products (e.g., electricity, fuels, virgin polymers, and lubricant oil). The analysis determines that the absorption of chlorine in columns with basic aqueous solutions is limited to plastics waste with PVC concentrations below 0.1%. Dissolution in ionic liquids is not cost-competitive. On the contrary, two-step processes with catalytic dechlorination followed by thermochemical catalytic depolymerization, either pyrolysis or hydrogenolysis, significantly improve process economics and emissions. The most economically viable alternative is hydrogenolysis for producing lubricants, while the technology with the lowest global warming potential is chemical recycling via catalytic pyrolysis.

circular economy↗
DOE OSTI2023

Methods of recovering an elemental rare earth metal, and methods of forming a rare earth metal

A method of recovering an elemental rare earth metal comprises placing a rare earth-containing material comprising a rare earth metal in a reaction solution comprising a reducing agent and a non-aqueous solvent comprising an ionic liquid or a eutectic mixture, reducing the rare earth metal with the reducing agent to form a metallic rare earth metal and cations of the reducing agent, transferring the cations of the reducing agent from the reaction solution to an electrochemical cell through an ion exchange membrane, and reducing the cations of the reducing agent in the electrochemical cell. Related methods of forming an elemental rare earth metal, and related systems are disclosed.

Case, Mary E.↗
DOE OSTI2021

A systematic study of lanthanide titanates (A 2 Ti 2 O 7 ) chemical durability: corrosion mechanisms and control parameters

Dense lanthanide titanates ranging from La 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 were synthesized by spark plasma sintering with similar micro-sized microstructure, and their chemical durability and degradation mechanisms were investigated by semi-dynamic leaching tests. Different corrosion mechanisms from incongruent to congruent dissolution were observed with preferential elemental releases of lanthanides in A 2 Ti 2 O 7 (A = La to Gd) and Ti in Er 2 Ti 2 O 7 and Yb 2 Ti 2 O 7 . Initial leaching was controlled by surface dissolution and long-term dissolution shifted to a diffusion-controlled mechanism for titanate pyrochlores from Sm 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 . Both short-term and long-term leaching rates decreased from La 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 , and materials became more corrosion resistant with decreasing ionic radius ratios of the rare-earth elements and titanium. Amorphous passivation films of several nm-thick enriched with Ti formed on the surfaces of the corroded materials, and the formation mechanisms were governed either by surface reorganization with preferential release of lanthanides or dissolution-precipitation from saturated bulk solutions with preferential release of titanium. Finally, these results demonstrate that the ionic size plays a dominant role in determining chemical durability of lanthanide titanates and a strong correlation is established among chemical composition/structural variation, passivation film formation and corrosion mechanisms, and materials chemical durability.

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

Non-Equilibrium Plasma Interactions with Biomaterials, Biological Solutions and Tissues

Cold atmospheric pressure plasma discharges offer an abundant source of reactive oxygen and nitrogen species (RONS) at room temperature enabling unique interactions with biomaterials, biological solutions and tissues. These interactions particularly with living matter are presently an important intellectual frontier in plasma science with promising potential applications ranging from human health care to advanced biomaterial processing. Exciting case studies have been reported that illustrate the huge potential of cold atmospheric plasma technology in wound healing and cancer treatment. The interaction of plasma with conducting and dielectric biomaterials such as tissue strongly influences the plasma properties. In turn this changes the impact of the plasma on the biomaterial. Particularly in the case of living matter, liquid based solutions are ubiquitous which complicates interfacial processes. The lack of insight into the underlying mechanisms of the interaction of plasma with wounds and tumors is currently a bottleneck for the further development of the technology and gives rise to many interesting scientific questions. This project was focused on plasma properties and kinetics during plasma-biomaterial interactions. Both DC pulsed and RF driven atmospheric pressure plasma jets, extensively used by the plasma community were studied. The bio-interfaces included hydrogel as a tissue model, (saline) solutions, bacteria and virus. Plasma diagnostics used include Thomson scattering, Rayleigh scattering, Raman scattering, (two-photon absorption) laser induced fluorescence, optical emission spectroscopy, absorption spectroscopy, molecular beam mass spectrometry and fast imaging allowing to determine electron densities and temperatures, ionic species, reactive species including radicals, gas temperatures, gas composition, electric fields and solution components transferred to the gas phase.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Deep Eutectic Solvents: A Review of Fundamentals and Applications

Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These green materials are promising for applications as inexpensive ’designer’ solvents exhibiting a host of tunable physicochemical properties. Here, a detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding behavior is postulated as the root cause of their melt-ing point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework for understanding DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies gainful research thrusts that would advance the field towards predictive models and fundamental understanding of these solvents.

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

Alkali Cation-Mediated Modulation of CO 2 Reduction Activity on Tin Electrodes in [EMIM][BF 4 ]/H 2 O Electrolytes

The development of efficient CO 2 reduction technologies hinges upon a thorough understanding of the intricate interplay between solution cations and the characteristics of the electrode surface. Recently, ionic liquids (ILs) have emerged as promising electrolytes for the CO 2 reduction reaction. However, the effect of alkali cations on the electrochemical CO 2 reduction (CO 2 R) reaction remains unclear in ILs. Here, in this report, we studied alkali cation effects by assessing the electrocatalytic CO 2 R activity with the IL 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water with alkali metal co-cations (i.e., Li + , Na + , and K + ) using a polycrystalline Sn catalyst. Contrary to previous findings in purely aqueous media with inorganic cations, where alkali cations strongly enhance CO 2 R via pH modulation and strengthening of interfacial electric fields, alkali cations in electrolytes containing the IL [EMIM][BF4] negatively impact CO 2 R activity on Sn electrodes. These results were attributed to the larger radius and higher concentration of the IL organic cation [EMIM] + that mitigates the impact of alkali cations. These findings highlight the complex interplay between IL cations and alkali metals in shaping CO 2 R performance.

Chemistry↗
DOE OSTI2026

Conformal hetero-electrolyte interface between soft oxyhalides and garnet enables low-pressure lithium-reservoir-free solid-state batteries

The operation of solid-state batteries with a lithium metal anode and a high voltage cathode requires solid electrolytes (SEs) that are chemically stable with lithium, have a wide electrochemical window, and accommodate volume changes in the electrodes. Unfortunately, no SE has exhibited satisfactory mechanical and electrochemical properties that fit these requirements to date. Dual solid electrolyte systems that use a different SE for the anolyte and catholyte present a viable solution. Here, we focus on oxyhalide SEs that demonstrate superior ionic conductivity and cathode compatibility, where their lithium metal reactivity and poor reduction stability can be resolved using a lithium garnet (Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 , LLZTO) separator. Nonetheless, this imposes a new hetero-electrolyte (H-E) interface at the anolyte|catholyte contact that defines the ion transport across the boundary. We report its promising properties, which are deconvoluted from the electrical measurements of bilayer symmetric cells, for three representative oxyhalide catholytes, LiNbOCl 4 , LiTaOCl 4 , and Li 3 Al 3 O 2 Cl 8 . Pressure-dependent measurements reveal that the relative softness of the oxyhalides (hardness ≤0.4 GPa) enables H-E resistances lower than 150 Ω cm 2 at 2–3 MPa. Mesoscale modelling reveals that the transfer-active contact area of oxyhalides with LLZTO is about 2–3-fold higher than that of argyrodite, Li 6 PS 5 Cl. The low H-E resistance of the LiNbOCl 4 |Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 dual electrolyte enables the cycling of a Li|LiNi 0.82 Mn 0.07 Co 0.11 O 2 full cell with a high discharge capacity (200 mA h g −1 ) at 60 °C and ∼7 MPa. Importantly, we demonstrate a Li-reservoir-free full cell with high Coulombic efficiency (>99.5%) and capacity at 1 MPa using this approach coupled with a garnet-silver interlayer.

Palmer, Max [University of California, Santa Barba↗
NASA NTRS1987

Soluble minerals in chemical evolution. II - Characterization of the adsorption of 5-prime-AMP and 5-prime-CMP on a variety of soluble mineral salts

The adsorption of 5-prime-AMP and 5-prime-CMP is studied in the saturated solutions of several mineral salts as a function of pH, ionic strength, and surface area of the solid salt. It is suggested that the adsorption which results from the binding between the nucleotide molecule and the salt surface is due to electrostatic forces. The adsorption is reversible in nature and decreases with increasing ionic strength.

Chan, Stephen↗
DOE OSTI2023

Structure–transport correlations in Na 11 Sn 2 SbSe 12 and its sulfide solid solutions

We report a new ion conductor—Na 11 Sn 2 SbSe 12 —as a possible candidate for a solid catholyte in composite cathodes for all-solid state Na-batteries, which exhibits a room temperature ionic conductivity of 0.15 ± 0.03 mS cm −1 and an activation energy of 0.39 ± 0.02 eV. The sulfide solid solutions of Na 11 Sn 2 SbSe 12 , namely, Na 11 Sn 2 SbS 12−x Se x (x = 1 and 6), were also investigated through a combination of Rietveld refinement against powder x-ray diffraction data and electrochemical impedance spectroscopy to reveal the complex structure–property relationships governing ion transport in this class of materials. Meanwhile, broadening of the Na-ion diffusion pathways in Na 11 Sn 2 SbSe 12 is expected to facilitate Na-ion transport compared to the sulfide-rich member of the solid solution, the opposite holds: increasing the Se fraction in Na 11 Sn 2 SbS 12−x Se x leads to a little change in the activation energy but a reduction in the ionic conductivity. We ascribe this to the lowering of the prefactor, σ 0 , in the Arrhenius relationship with increasing lattice “softening” as a function of higher Se content.

Ramos, Erika P.↗
DOE OSTI2025

Alkali Cation Inhibition of Imidazolium-Mediated Electrochemical CO 2 Reduction on Silver

Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.

cations↗
DOE OSTI2025

Investigating the quaternary structure of a homomultimeric catechol 1,2-dioxygenase: An integrative structural biology study

The structural analysis of catechol 1,2 dioxygenase from Stutzerimonas frequens GOM2, SfC12DO, was conducted using various structural techniques. SEC-SAXS experiments revealed that SfC12DO, after lyophilization and reconstitution processes, can form multiple enzymatically active oligomers, including dimers, tetramers, and octamers. These findings differ from previous studies, which reported active dimers in homologous counterparts with available crystallographic structures, or trimers observed exclusively in solution for SfC12DO and its homologous isoA C12DO from Acinetobacter radioresistens under low ionic strength conditions. In some cases, tetramers were also reported, such as for the Rodococcus erythropolis C12DO. The combined results of Small-Angle X-ray Scattering, Dynamic Light Scattering, and Transmission Electron Microscopy experiments provided additional insights into these active oligomers’ shape and molecular organization in an aqueous solution. These results highlight the oligomeric structural plasticity of SfC12DO, proving that it can exist in different oligomeric forms depending on the physicochemical characteristics of the solutions in which the experiments were performed. Remarkably, regardless of its oligomeric state, SfC12DO maintains its enzymatic activity even after prior lyophilization. All these characteristics make SfC12DO a putative candidate for bioremediation applications in polluted soils or waters.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2004

Solution Preserves Nucleic Acids in Body-Fluid Specimens

A solution has been formulated to preserve deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) in specimens of blood, saliva, and other bodily fluids. Specimens of this type are collected for diagnostic molecular pathology, which is becoming the method of choice for diagnosis of many diseases. The solution makes it possible to store such specimens at room temperature, without risk of decomposition, for subsequent analysis in a laboratory that could be remote from the sampling location. Thus, the solution could be a means to bring the benefits of diagnostic molecular pathology to geographic regions where refrigeration equipment and diagnostic laboratories are not available. The table lists the ingredients of the solution. The functions of the ingredients are the following: EDTA chelates divalent cations that are necessary cofactors for nuclease activity. In so doing, it functionally removes these cations and thereby retards the action of nucleases. EDTA also stabilizes the DNA helix. Tris serves as a buffering agent, which is needed because minor contaminants in an unbuffered solution can exert pronounced effects on pH and thereby cause spontaneous degradation of DNA. SDS is an ionic detergent that inhibits ribonuclease activity. SDS has been used in some lysis buffers and as a storage buffer for RNA after purification. The use of the solution is straightforward. For example, a sample of saliva is collected by placing a cotton roll around in the subject's mouth until it becomes saturated, then the cotton is placed in a collection tube. Next, 1.5 mL of the solution are injected directly into the cotton and the tube is capped for storage at room temperature. The effectiveness of the solution has been demonstrated in tests on specimens of saliva containing herpes simplex virus. In the tests, the viral DNA, as amplified by polymerase chain reaction, was detected even after storage for 120 days.

Pierson, Duane L.↗
DOE OSTI2023

High-entropy halide perovskite single crystals stabilized by mild chemistry

High entropy materials are excellent candidates for a range of functional materials but traditionally require high-temperature synthetic procedures over 1000°C and complex processing techniques such as hot rolling to form. One route to address the extreme synthetic requirements for high entropy materials should involve designing crystal structures with ionic bonding networks and low cohesive energies. Here, we develop room-temperature (20°C) and low temperature (80°C) solution synthesis procedures for a new class of metal-halide perovskite high entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of the class of metal-halide perovskites, these HES single crystals are designed on the cubic Cs 2 MCl 6 (M = Zr 4+ , Sn 4+ , Te 4+ , Hf 4+ , Re 4+ , Os 4+ , Ir 4+ , or Pt 4+ ) vacancy-ordered double perovskite structure from the self-assembly of stabilized complexes in multielement inks, namely free Cs + cations and five or six different isolated [MCl6] 2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five- and six-elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs 2 MCl 6 crystal structure and stoichiometry maintained. In conclusion, the incorporation of various [MCl 6 ] 2- octahedral molecular orbitals disordered across the high entropy five- and six-element Cs 2 MCl 6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

36 MATERIALS SCIENCE↗