Search NASA⌕ Search

SEARCH · Search NASA

Results for “aqueous solution”

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 271 records · Page 15

Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures

We have performed classical molecular dynamics (MD) simulations of aqueous sodium chloride (NaCl) solutions from 298 to 674 K at 200 bars to understand the influence of ion pairing and ion self-diffusion on electrical conductivity in high-temperature/high-pressure salt solutions. Conductivity data obtained from the MD simulation highlight an apparent anomaly, namely, a conductivity maximum as temperature increases along an isobar, which has been also observed in experimental studies. By examining both velocity autocorrelation and cross-correlation terms of the Green-Kubo integral, we quantitatively demonstrate that the conductivity anomaly arises mainly from a competition between the single-ion self-diffusion and the contact ion pair formation. The velocity autocorrelation function in conjunction with structural analysis suggests that diffusive motion of ions is suppressed at high temperatures due to the persistence of an inner hydration shell. Here, the contribution of velocity cross-correlation functions between oppositely charged ions becomes significant at the onset of the conductivity decrease. Structural analysis based on Voronoi tessellation and pair correlation functions indicates that the fraction of contact ion pairs increases as temperature increases. Spatial decomposition of the electrical conductivity also indicates that the formation of contact ion pairs significantly decreases the electrical conductivity compared to Nernst-Einstein conductivity, but the contribution of distant opposite charges cannot be ignored except at the highest temperature due to unscreened long-range interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon nanotube scanning probe for imaging in aqueous environment

Carbon nanotubes (CNTs) used as a probe for scanning probe microscopy has become one of the many potential usages of CNTs that is finding real applications in scientific research and industrial communities. It has been proposed that the unique mechanical buckling properties of the CNT would lessen the imaging force exerted on the sample and, thus, make CNT scanning probes ideal for imaging soft materials, including biological samples in liquid environments. The hydrophobic nature of the CNT graphitic sidewall is clearly chemically incompatible with the aqueous solution requirements in some biological imaging applications. In this paper, we present electron micrograph results demonstrating the instability of CNT scanning probes when submerged in aqueous solution. Moreover, we also introduce a novel approach to resolve this chemical incompatibility problem. By coating the CNT probe with ethylenediamine, thus rendering the CNT probe less hydrophobic, we demonstrate the liquid imaging capability of treated CNT probes. Experimental data for imaging in aqueous solutions are presented, which include an ultrathin Ir film and DNA molecules on a mica surface.

Microscopy, Atomic Force/methods↗

Biosorption of Uranium by Bone Meal

The treatment of aqueous solution waste containing organic compounds and radionuclides has always been a great concern since the processes available are usually expensive and unfeasible for the low volume of radioactive liquid waste recovered. In view of a more efficient and low cost treatment, biosorption-based technologies for the removal of this hazardous radionuclides, heavy metals, and organic substances from contaminated matrices have been studied as an alternative process. In this context, bone meal is the material of choice, and contains calcium phosphate in the form of hydroxyapatite. Previous studies with hydroxyapatite showed that this material is efficient in removing heavy metals from polluted soils due to its adsorbing ability. In this context, uranium biosorption capacity by using bone meal was evaluated by different experimental conditions. This study aims at analyzing the capacity of bone meal to remove uranium from aqueous solution through biosorption process, considering that this nuclide is radiotoxic and may cause serious environmental problems and risks to human life if not correctly disposed. The biosorption capacity of U by bone meal was evaluated under different experimental conditions. The results suggested that adsorption with this material can be applied in the treatment of aqueous solutions as a low-cost and highly efficient alternative to remove U. Therefore, we believe that our results are useful for other investigators dealing with similar problems. Further work is required to evaluate this material as a potential adsorbent concerning the treatment of liquid organic radioactive waste containing uranium. Next studies are crucial to ascertain the biosorption efficiency, by analyzing other variables, such as adsorbent dosage, pH and temperature.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stress Corrosion Cracking of NaSICON Membranes in Aqueous Electrolytes for Redox-Flow Batteries

The sodium super-ionic conductor (NaSICON) has versatile applications as a ceramic electrolyte for energy storage, where it can serve as an impermeable separator in solid-state batteries and redox flow systems. In particular, NaSICON systems have been proposed to be relatively stable in contact with water, making them compatible with aqueous battery chemistries. However, owing to their brittle nature and metal oxide constituents, stress-corrosion cracking (SCC) is an important failure mechanism that has not been previously explored. In this study, we assess the fracture toughness of NaSICON membranes in contact with aqueous solutions that are relevant to redox flow systems. Microindentation was performed to generate visible surface cracks and residual stress, which were observed to grow in length after exposure to aqueous solutions. This allows for a quantitative measurement of fracture toughness, which decreases after exposure to water. To contextualize these results, we develop a simplified model of the fracture behavior in aqueous redox-flow batteries that incorporate NaSICON membranes, illustrating the importance of SCC in cell design. This work provides quantitative insights into SCC as a failure mode in NaSICON, enhancing our understanding of the chemo-mechanical behavior of ceramic electrolytes in contact with aqueous solutions.

Zhang, Mengyao↗

Insights into determining pore size properties of ultrafiltration membranes

The selectivity of porous membranes is often characterized using solute rejection tests, where membranes are challenged with dilute aqueous solutions of neutral solutes at operating conditions that minimize concentration polarization and fouling. In single solute tests, a membrane is challenged with one molecular weight (MW) solute at a time from low to high MW. Since single solute methods are time-intensive, mixed solute tests have become more common, where a mixture of several MW solutes challenges a membrane at once. However, the presence of large solutes in a mixture increases the rejection of smaller solutes. Furthermore, there are no universally accepted operating conditions or standard methods used by membrane manufacturers or researchers for the experiments, leading to difficulty in pore size and pore characteristic comparisons. In this paper, commercial ultrafiltration membranes were challenged with single and mixed solute polyethylene glycol (PEG) and dextran aqueous solutions. First, rejection values determined using total organic carbon (TOC) and high-performance liquid chromatography (HPLC) from single solute filtration experiments are compared. Differences in rejection curves obtained by the two techniques are attributed to solute polydispersity. Mixed solute filtration experiments with binary mixtures of solutes showcased co-solute interactions, which increase with both the size and weight percent of large solute in the mixture. Mixed solute filtration experiments at varying operating conditions (i.e., stir speed and flux) were conducted to determine operating conditions that mitigate co-solute interactions. Stir speed had a minimal effect on co-solute interactions. In contrast, low flux conditions can help minimize co-solute interactions, leading to pore size distributions that closely resemble results observed in single solute filtration using narrowly dispersed solutes. Additionally, at low flux conditions, the predicted membrane pore size distributions utilizing mixed solute experiments with PEG and dextran were similar.

36 MATERIALS SCIENCE↗

Electrocatalysts, and fuel cells containing them

Provided are electrocatalysts, fuel cells, methods of making fuel cells, and methods of generating an electric current, each featuring a platinum (Pt)-containing substrate in contact with an aqueous solution comprising Pb2+. Electrocatalysts of the invention are formed via underpotential deposition (UPD) when a trace amount of Pb2+ is present in the electrolyte of a half anodic cell for oxidizing formic acid using Pt as the anode. Surprisingly, the UPD process dramatically enhances the activity of formic acid oxidation, at least as much as 10-fold compared with palladium (Pd) black. In an embodiment, the electrocatalyst comprises a Pt-containing substrate, a submonolayer of lead (Pb) adsorbed onto the Pt-containing substrate, and an aqueous solution comprising Pb2+, wherein the concentration of Pb2+ in the aqueous solution is 10 to 500 μm.

30 DIRECT ENERGY CONVERSION↗

A new capability for investigating the structure and dynamics of liquids at high pressures

Water and aqueous solutions are critical to many areas of science and technology. As a result, tremendous effort has been devoted to understanding them in detail. Despite over a century of research, fundamental questions about water and aqueous solutions remain unanswered. However, an intriguing possibility – that liquid water can exist in two thermodynamically distinct states – has emerged as the most likely explanation. The problem is that experimental confirmation of this hypothesis requires experiments on water at high pressures and low temperatures, conditions in which liquid water only exists briefly before turning into crystalline ice. This project investigated the feasibility of developing a new capability for study water and aqueous solutions under these challenging conditions. The physical constraints, such as the timescales for crystallization and thermal diffusion in supercooled water, were evaluated along with their impact on the design criteria for the instrument. Several basic design options were considered that could meet the technical requirements. The options were also evaluated with respect to their use of commercially available equipment versus the need for custom designs or in-house development. The project identified two viable options to pursue. The first option would use a high-pressure syringe pump in conjunction with fused silica (or sapphire) capillaries. The second option would use a diamond anvil cell. These options can both be used with optical spectroscopies, such as Raman or Infrared.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Fast extraction of nickel from aqueous media by using ionic metal-organic frameworks

As global demand for stainless steel rapidly increases, supply for minerals such as nickel, manganese, and chromium become more critical. To shift mineral peak production and delay scarcity of alloying minerals, recycling rate of the mineral needs to increase. Development of simple and cost-effective techniques for critical mineral production and recovery from industrial wastewater will lead to enhance the current recycling rate of the mineral and reduce potential hazards of industrial wastewater bearing high concentrations of minerals. Here, in this study, ionic metal-organic framework (iMOF)-based sorbents are successfully designed for critical metal ion extraction from aqueous solution. The iMOFs are highly stable in aqueous solution over wide pH ranges, indicating that they are suitable for use in industrial wastewater with harsh chemical environments. The sorption capacity of iMOFs towards Ni reaches 34.1 mg/g with a removal efficiency of >99.9%. Notably, complete extraction of Ni takes place within 5 min, which is much faster compared to other sorbents. Moreover, the iMOFs can simultaneously coextract multiple minerals, proving their effectiveness as general sorbents for critical mineral recovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Melanoidin and aldocyanoin microspheres - Implications for chemical evolution and early Precambrian micropaleontology

Two new classes of organic microspheres are described. One of them (melanoidin) is synthesized from amino acids and sugars in heated aqueous solutions. The other (aldocyanoin) is formed in aqueous solutions of ammonium cyanide and formaldehyde at room temperature. The general properties of these microspheres, including conditions of synthesis, size and shape, mechanical and pH stability, and solubility, are compared with corresponding properties of other protocell model systems. It is concluded that melanoidin and aldocyanoin microspheres are plausible candidates for precellular units in the primitive hydrosphere. Since the bulk of the organic carbon in early Precambrian sediments is insoluble kerogen-melanoidin, it is suggested that some Precambrian microfossils may be abiotic melanoidin microspheres.

Kenyon, D. H.↗

Alloy based electrochemical catalyst for conversion of carbon dioxide to hydrocarbons

An electrocatalyst comprising (i) carbon nanospikes and (ii) copper alloy nanoparticles containing copper and at least one noble metal and residing on and/or between the carbon nanospikes. Also disclosed herein is a method of producing the electrocatalyst. Also described herein is a method for converting carbon dioxide into hydrocarbons by use of the above-described electrocatalyst. The method for producing hydrocarbons more specifically involves contacting the electrocatalyst with an aqueous solution of a bicarbonate salt while the aqueous solution is in contact with a source of carbon dioxide, and electrically powering the electrocatalyst as a cathode at negative potential condition while the cathode is in electrical communication with a counter electrode electrically powered as an anode, to convert the carbon dioxide into hydrocarbons containing at least four carbon atoms and composed of only carbon and hydrogen.

Rondinone, Adam J.↗

Probing the Structure and Dynamics of Fluid Mixtures in Porous Materials Through Ultrafast Vibrational Spectro-Microscopy and Many-Body Molecular Dynamics

This research program focused on the characterization of both molecular structure and dynamics of aqueous solutions in various metal-organic frameworks (MOFs) and organic polymers that have recently been proposed for applications in water treatment technologies. This was accomplished by integrating ultrafast vibrational spectroscopy and microscopy, which are sensitive to local environments, molecular orientation, and dynamical couplings, with many-body molecular dynamics (MB-MD) simulations, which enable realistic modeling of aqueous systems and porous materials under different thermodynamic conditions. Our studies allowed for identifying the physical mechanisms and characterizing the underlying molecular interactions between water and host materials that determine the adsorption and transport processes of water in various MOFs and β-cyclodextrin polymers – prototypical examples of porous materials and polymers, that have recently been proposed for technological applications in water purification. By combining bulk- and surface-sensitive, spatially resolved ultrafast vibrational spectroscopy with MB-MD simulations, it was possible to gain broad insight into the structure and mobility of water under heterogeneous confinement at various length scales. In particular, measurements of surface- and bulk-sensitive vibrational spectra at single crystal level, integrated with MB-MD simulations were used to characterize domain-specific, structure–binding affinity relationships. Besides providing specific information about the behavior of aqueous solutions in prototypical MOFs and organic polymers for potential applications in water treatment technologies, our studies also provided fundamental insights into the properties of aqueous solutions in confined heterogeneous environments, which have broad implications in many areas, ranging from heterogeneous catalysis to oil recovery, ion transport processes, and reaction-diffusion processes in crowded systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solution Chemistry of Copper(II) Binding to Substituted 8-Hydroxyquinolines

8-Hydroxyquinolines (8HQs) are a family of lipophilic metal ion chelators that have been used in a range of analytical and pharmaceutical applications over the last 100 years. More recently, CQ (clioquinol; 5-chloro-7-iodo-8-hydroxyquinoline) and PBT2 (5,7-dichloro-2-[(dimethylamino)methyl]-8-hydroxyquinoline) have undergone clinical trials for the treatment of Alzheimer’s disease and Huntington’s disease. Because CQ and PBT2 appear to redistribute metals into cells, these compounds have been redefined as copper and zinc ionophores. Despite the attention surrounding the clinical trials and the clear link between 8HQs and metals, the fundamental solution chemistry of how these compounds bind divalent metals such as copper and zinc, as well as their mechanism(s) of action in mammalian systems, remains poorly understood. Here, we used a combination of X-ray absorption spectroscopy (XAS), high-energy resolution fluorescence detected (HERFD) XAS, electron paramagnetic resonance (EPR), and UV–visible absorption spectroscopies to investigate the aqueous solution chemistry of a range of 8HQ derivatives. To circumvent the known solubility issues with 8HQ compounds and their complexes with Cu(II), and to avoid the use of abiological organic solvents, we have devised a surfactant buffer system to investigate these Cu(II) complexes in aqueous solution. Our study comprises the first comprehensive investigation of the Cu(II) complexes formed with many 8HQs of interest in aqueous solution, and it provides the first structural information on some of these complexes. We find that halogen substitutions in 8HQ derivatives appear to have little effect on the Cu(II) coordination environment; 5,7-dihalogenated 8HQ conformers all have a pseudo square planar Cu(II) bound by two quinolin-8-olate anions, in agreement with previous studies. Conversely, substituents in the 2-position of the 8HQ moiety appear to cause significant distortions from the typical square-planar-like coordination of most Cu(II)-bis-8HQ complexes, such that the 8HQ moieties in the Cu(II)-bis-8HQ complex are rotated approximately 30–40° apart in a “propeller-like” arrangement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Here aqueous solubilization of hydrophobic tetrapyrrole macrocycles by attachment to an amphiphilic single-chain nanoparticle (SCNP)

Solubilization of hydrophobic tetrapyrrole macrocycles and other fluorophores in aqueous solution has been achieved by covalent attachment to the terminus of an amphiphilic polymer, thereby affording a single-fluorophore–single-chain nanoparticle (SCNP). The polymer is a heterotelechelic random polyacrylate/polyacrylamide copolymer bearing hydrophobic and hydrophilic pendant groups. The polymer has a folded unimeric morphology (~13 nm hydrodynamic diameter) in 1 M NaCl aqueous solution as indicated by dynamic light-scattering spectroscopy. Five hydrophobic organic fluorophores (coumarin, perylene, two chlorins, one phthalocyanine) have been synthesized with a conjugatable tether. Covalent conjugation of the fluorophore–maleimide to the polymer terminus via thiol–maleimide reaction was carried out in DMF. The resulting fluorophore–SCNP in 1 M NaCl aqueous solution exhibited retained spectral features and fluorescence quantum yield comparable to those of the respective hydrophobic benchmark in toluene. This single-fluorophore–single-polymer strategy simplifies the challenging and often idiosyncratic syntheses of water-soluble tetrapyrrole macrocycles by using the polymer as a general aqueous solubilization package, and in so doing opens up opportunities for the application of hydrophobic fluorophores in the life sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Method of evaluating pH using a metallic nanoparticle incorporated nanocomposite-based optical pH sensor

A method for evaluating the pH of an aqueous solution by utilizing the optical properties of a pH sensing material comprised of plurality of optically active nanoparticles dispersed in matrix material. The optically active nanoparticles have an electronic conductivity greater than about 10−1 S/cm and generally have an average nanoparticle diameter of less that about 500 nanometers, and the matrix material is a material which experiences a change in surface charge density over a pH range from 2.0 to 12.0 of at least 1%. The method comprises contacting the pH sensing material and the aqueous solution, illuminating the pH sensing material, and monitoring an optical signal generated through comparison of incident light and exiting light to determine the optical transmission, absorption, reflection, and/or scattering of the pH sensitive material. The optical signal of the pH sensitive material varies in response to the pH of the aqueous solution.

Ohodnicki, Jr., Paul R.↗

CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands

In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Linear relationships for modeling CO 2 absorption in aqueous alkanolamine solutions in a thermodynamically consistent way

A thermodynamically consistent model for the carbon dioxide (CO 2 ) absorption in aqueous alkanolamine system is of great importance in the research and development of a CO 2 capture process. To facilitate the development of thermodynamic models, linear Gibbs free energy, enthalpy, and heat capacity relationships using well-known amines as reference are used to correlate the standard reference state properties of ionic species with those of molecular species in the electrolyte system, which has been approved to provide a reliable and consistent way to estimate required parameters when there is minimal or no appropriate experimental data available. Here, the proposed relationships have been applied to the development of an electrolyte nonrandom two liquid (NRTL) activity coefficient model for CO 2 absorption in aqueous 1-amino-2-propanol (A2P) solution, as an example to demonstration the methodology. With limited vapor–liquid equilibrium data and other thermodynamic properties, the parameters in the electrolyte NRTL model are identified with good accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aryl Diazonium-Assisted Amidoximation of MXene for Boosting Water Stability and Uranyl Sequestration via Electrochemical Sorption

Despite that two-dimensional transition metal carbides and carbonitrides (MXenes) are burgeoning candidates for remediation of environmental pollutants, the construction of robust functionalized MXene nanosheets with a high affinity for target heavy metal ions and radionuclides remains a challenge. Here we report the successful placement of amidoxime chelating groups on Ti 3 C 2 T x MXene surface by diazonium salt grafting. The introduction of amidoxime functional groups significantly enhances the selectivity of Ti 3 C 2 T x nanosheets for uranyl ions and also greatly improves their stability in aqueous solution, enabling efficient, rapid, and recyclable uranium extraction from aqueous solutions containing competitive metal ions. Benefiting from the excellent conductivity of MXenes, the amidoxime functionalized Ti 3 C 2 T x nanosheets show outstanding electrochemical performance such that when loaded on carbon cloth the application of an electric field increases the uranium adsorption capacity from 294 to 626 mg/g, outperforming all organic electrochemical sorption materials reported previously. Finally, the present work provides an effective strategy to functionalize MXene nanosheets with fundamental implications for the design of MXene-based selective electrosorption electrode materials.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Predicting Radiation-Induced Plutonium Redox Chemistry using Multi-scale Modeling Methods

Over the the last 70 years plutonium (Pu) has been integral in the development of several technologies that have changed the world, yet our fundamental understanding of its chemistry is still far from complete. This is a testament to this element’s unique and complex properties, such as its ability to coexist as multiple oxidation states in aqueous solution. Careful manipulation of plutonium oxidation states is essential in the study and utilization of its rich chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. For this reason, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded negligible net change in the steady-state oxidation state distribution of Pu(IV). Multi-scale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to radiation-induced redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by radiolytic nitrous acid and hydrogen peroxide, and the oxidation of Pu(III) by nitrate and hydroxyl radicals. These radiation-induced redox processes are augmented by plutonium’s inherent disproportionation reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗