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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Effect of Anions on the Delithiation of [Li–Al] Layered Double Hydroxides: Thermodynamic Insights

The utilization of lithium aluminum [Li–Al] layered double hydroxides (LDHs) is explored for direct lithium extraction (DLE) from geothermal brines and minerals. Following extraction, the Li + ions need to be removed from the LDH structure and converted into LiOH or Li 2 CO 3 products, making them suitable for battery applications. The research investigates the delithiation of [Li–Al-X] LDHs (where X = Cl – , OH – , and SO 4 2– ), which were synthesized and dried under different conditions. Herein the study aims to understand how the choice of anions and drying conditions affects the delithiation process. To determine the stability of these [Li–Al] LDHs, high-temperature oxide melt solution calorimetry is employed. The results reveal that the stability of LDHs varies significantly based on postdrying conditions, anion choice, and the water content in the interlayer. The order of stability, as indicated by the enthalpy of formation values, is found to be OH-LDH-O > OH-LDH-A > SO 4 -LDH-O > SO4-LDH-A > Cl-LDH-O > Cl-LDH-A. This trend is attributed to the interactions among the interlayer species and the metal hydroxide layers.

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

Physicochemical control of solvation and molecular assembly of charged amphiphilic oligomers at air-aqueous interfaces

Hypothesis : Understanding the rules that control the assembly of nanostructured soft materials at interfaces is central to many applications. We hypothesize that electrolytes can be used to alter the hydration shell of amphiphilic oligomers at the air-aqueous interface of Langmuir films, thereby providing a means to control the formation of emergent nanostructures. Experiments : Three representative salts – (NaF, NaCl, NaSCN) were studied for mediating the self-assembly of oligodimethylsiloxane methylimidazolium (ODMS-MIM + ) amphiphiles in Langmuir films. The effects of the different salts on the nanostructure assembly of these films were probed using vibrational sum frequency generation (SFG) spectroscopy and Langmuir trough techniques. Experimental data were supported by atomistic molecular dynamic simulations. Findings : Langmuir trough surface pressure – area isotherms suggested a surprising effect on oligomer assembly, whereby the presence of anions affects the stability of the interfacial layer irrespective of their surface propensities. In contrast, SFG results implied a strong anion effect that parallels the surface activity of anions. These seemingly contradictory trends are explained by anion driven tail dehydration resulting in increasingly heterogeneous systems with entangled ODMS tails and appreciable anion penetration into the complex interfacial layer comprised of headgroups, tails, and interfacial water molecules. These findings provide physical and chemical insight for tuning a wide range of interfacial assemblies.

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

Ion Pairing and Molecular Orientation at Liquid/Liquid Interfaces: Self-Assembly and Function

We report that molecular orientation plays a pivotal role in defining the functionality and chemistry of interfaces, yet accurate measurements probing this important feature are few, due, in part, to technical and analytical limitations in extracting information from molecular monolayers. For example, buried liquid/liquid interfaces, where a complex and poorly understood balance of inter- and intramolecular interactions impart structural constraints that facilitate the formation of supramolecular assemblies capable of new functions, are difficult to probe experimentally. Here, we use vibrational sum-frequency generation spectroscopy, numerical polarization analysis, and atomistic molecular dynamics simulations to probe molecular orientations at buried oil/aqueous interfaces decorated with amphiphilic oligomers. We show that the orientation of self-assembled oligomers changes upon the addition of salts in the aqueous phase. The evolution of these structures can be described by competitive ion effects in the aqueous phase altering the orientations of the tails extending into the oil phase. These specific anionic effects occur via interfacial ion pairing and associated changes in interfacial solvation and hydrogen-bonding networks. These findings provide more quantitative insight into orientational changes encountered during self-assembly and pave the way for the design of functional interfaces for chemical separations, neuromorphic computing applications, and related biomimetic systems.

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

Influence of uranyl complexation on the reaction kinetics of the dodecane radical cation with used nuclear fuel extraction ligands (TBP, DEHBA, and DEHiBA)

Specialized extractant ligands – such as tri-butyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-2-ethylhexylisobutryamide (DEHiBA) – have been developed for the recovery of uranium from used nuclear fuel by reprocessing solvent extraction technologies. These ligands must function in the presence of an intense multi-component radiation field, and thus it is critical that their radiolytic behaviour be thoroughly evaluated. This is especially true for their metal complexes, where there is negligible information on the influence of complexation on radiolytic reactivity, despite the prevalence of metal complexes in used nuclear fuel reprocessing solvent systems. Here we present a kinetic investigation into the effect of uranyl (UO 2 2+ ) complexation on the reaction kinetics of the dodecane radical cation (RH˙ + ) with TBP, DEHBA, and DEHiBA. Complexation had negligible effect on the reaction of RH˙ + with TBP, for which a second-order rate coefficient (k) of (1.3 ± 0.1) × 10 10 M -1 s -1 was measured. For DEHBA and DEHiBA, UO 2 2+ complexation afforded an increase in their respective rate coefficients: k(RH˙ + + [UO 2 (NO 3 ) 2 (DEHBA) 2 ]) = (2.5 ± 0.1) × 10 10 M -1 s -1 and k(RH˙ + + [UO 2 (NO 3 ) 2 (DEHiBA) 2 ]) = (1.6 ± 0.1) × 10 10 M -1 s -1 . This enhancement with complexation is indicative of an alternative RH˙ + reaction pathway, which is more readily accessible for [UO 2 (NO 3 ) 2 (DEHBA) 2 ] as it exhibited a much larger kinetic enhancement than [UO 2 (NO 3 ) 2 (DEHiBA) 2 ], 2.6× vs. 1.4×, respectively. Complementary quantum mechanical calculations suggests that the difference in reaction kinetic enhancement between TBP and DEHBA/DEHiBA is attributed to a combination of reaction pathway (electron/hole transfer vs. proton transfer) energetics and electron density distribution, wherein attendant nitrate counter anions effectively ‘shield’ TBP from RH˙ + electron transfer processes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Role of Protein-Water Interface in the Stacking Interactions of Granum Thylakoid Membranes—As Revealed by the Effects of Hofmeister Salts

The thylakoid membranes of vascular plants are differentiated into stacked granum and unstacked stroma regions. The formation of grana is triggered by the macrodomain formation of photosystem II and light-harvesting complex II (PSII-LHCII) and thus their lateral segregation from the photosystem I—light-harvesting complex I (PSI-LHCI) super-complexes and the ATP-synthase; which is then stabilized by stacking interactions of the adjacent PSII-LHCII enriched regions of the thylakoid membranes. The self-assembly and dynamics of this highly organized membrane system and the nature of forces acting between the PSII-LHCII macrodomains are not well understood. By using circular dichroism (CD) spectroscopy, small-angle neutron scattering (SANS) and transmission electron microscopy (TEM), we investigated the effects of Hofmeister salts on the organization of pigment-protein complexes and on the ultrastructure of thylakoid membranes. We found that the kosmotropic agent (NH 4 ) 2 SO 4 and the Hofmeister-neutral NaCl, up to 2 M concentrations, hardly affected the macro-organization of the protein complexes and the membrane ultrastructure. In contrast, chaotropic salts, NaClO 4 , and NaSCN destroyed the mesoscopic structures, the multilamellar organization of the thylakoid membranes and the chiral macrodomains of the protein complexes but without noticeably affecting the short-range, pigment-pigment excitonic interactions. Comparison of the concentration- and time-dependences of SANS, TEM and CD parameters revealed the main steps of the disassembly of grana in the presence of chaotropes. It begins with a rapid diminishment of the long-range periodic order of the grana membranes, apparently due to an increased stacking disorder of the thylakoid membranes, as reflected by SANS experiments. SANS measurements also allowed discrimination between the cationic and anionic effects—in stacking and disorder, respectively. This step is followed by a somewhat slower disorganization of the TEM ultrastructure, due to the gradual loss of stacked membrane pairs. Occurring last is the stepwise decrease and disappearance of the long-range chiral order of the protein complexes, the rate of which was faster in LHCII-deficient membranes. These data are interpreted in terms of a theory, from our laboratory, according to which Hofmeister salts primarily affect the hydrophylic-hydrophobic interactions of proteins, and the stroma-exposed regions of the intrinsic membrane proteins, in particular—pointing to the role of protein-water interface in the stacking interactions of granum thylakoid membranes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

High-Energy and Stable Subfreezing Aqueous Zn–MnO 2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO 2

One major challenge of aqueous Zn–MnO 2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here, in this study, the use of simple Zn(ClO 4 ) 2 aqueous electrolytes is described for all-weather Zn–MnO 2 batteries even down to -60 °C. The symmetric, bulky ClO 4 - anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g -1 on MnO 2 cathodes at -30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO 2 cathode from unstable H+ insertion to predominantly pseudocapacitive Zn 2+ insertion, which converts MnO 2 nanofibers into complicated zincated MnO x that are largely disordered and appeared as crumpled paper sheets. The Zn 2+ insertion at -30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn 2+ additives. In addition, simple Zn(ClO 4 ) 2 electrolyte also enables a nearly fully reversible and dendrite-free Zn anode at -30 °C with ≈98% Coulombic efficiency. Zn–MnO 2 prototypes with an experimentally verified unit energy density of 148 Wh kg -1 at a negative-to-positive ratio of 1.5 and an electrolyte-to-capacity ratio of 2.0 are further demonstrated.

25 ENERGY STORAGE↗
DOE OSTI2020

Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated under suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. In this paper, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl–SO 4 –HCO 3 anion effects. Emergence of Lp/Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions without HCO 3 – ; whereas Lp and Gt concomitantly nucleate in SO 4 2– -rich solutions, and also when co-solute HCO 3 – is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO 4 ) or acicular needle-shaped (in HCO 3 ) Gt crystals nucleate and grow radially outward from the Fh aggregates. Stages of transformation monitored by in situ μ-XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by the onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelmingly support dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that the iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Effect of Tethering Anions in Block Copolymer Electrolytes via Molecular Dynamics Simulations

Ion-containing block copolymers (BCPs) are promising solid-state electrolytes as they can combine ion conduction and mechanical robustness via multiple microphases. However, salt-doped BCPs can have low ion conduction and transference number. One strategy to increase transference number is to tether anions to the polymer backbone (creating a single-ion conductor), though this may impact cation mobility. Leveraging coarse-grained molecular dynamics simulations, we compare the effects of ion concentration and polymer dielectric constant on BCPs with and without bonding anions to the chain (without changing any other chemical properties). We find that single-ion BCPs have higher cation conductivity than analogous salt-doped BCPs, especially at moderate ion concentrations. Furthermore, we also compare several structural features of these systems; notably, tethering anions causes the ions to spread more evenly throughout the conducting phase, which is related to improved cation conduction.

25 ENERGY STORAGE↗
DOE OSTI2025

Effect of Fluoride Anions on Nd(III) Electrode Processes and Nd Metal Recovery in LiCl–KCl–NdCl 3

Here, this work investigated the impact of fluoride anions on Nd metal recovery in LiCl–KCl–NdCl 3 electrolytes by introducing LiF at a molar F/Nd ratio of 9 at 773 K. The voltammetric measurements confirmed that the fluoride ions facilitated single-step Nd(III)/Nd reduction by promoting the stability of the Nd(III) state compared to two-step reduction (Nd(III)/Nd(II) and Nd(II)/Nd) in all-chloride electrolytes. The stabilized Nd(III) state in the LiF-containing electrolyte effectively suppressed partial Nd(III)/Nd(II) reduction and the back-dissolution of Nd metal via comproportionation. By suppressing these reactions, high round-trip Coulombic efficiencies of 77–86% were achieved in the LiF-containing electrolyte during selective Nd deposition–removal cycles compared to 53–59% in all-chloride electrolytes. The Faradaic yield for Nd metal recovery was estimated at 38.6% in the LiF-containing electrolyte following long-term electrolysis, more than three times higher than 11.3% in all-chloride electrolytes. These results confirm the beneficial effect of fluoride ions on Nd metal recovery in low-melting chloride-based electrolytes, promising efficient Nd recovery at low temperatures.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

Achieving stable, selective single-atom catalysts is challenging because localsurface-site structures are difficult to control. Surface organometallic chemistry and organic−inorganic hybrid materials offer partial solutions, but applications to supporting zero-valent metals are limited. We demonstrate that well-defined, ionically bound N-heterocyclic phosphenium ([NHP] + ) ligands can be generated on silylium-functionalized sulfated zirconia ([ i Pr 3 Si][SZO]). These surface-bound [NHP][SZO] ligands coordinate Pt(0) centers, forming [(NHP)Pt(0)L][SZO] precatalysts that are highly active for alkyne hydrosilylation. Systematic studies reveal that sterically bulky aromatic ligands enhance regioselectivity, achieving performances comparable to molecular Pt catalysts. Further, more-coordinating anions support more-regioselective precatalysts; therefore, SZO supports more-selective species than weaker-coordinating Al(OC(CF 3 ) 3 ) 3 - functionalized silica, a trend confirmed by molecular analogues. These results demonstrate that both the ligand and support control catalytic behavior and enable solid-state structure− activity relationships.

Catalysts↗
DOE OSTI2023

Anion exchange membranes: The effect of reinforcement in water and electrolyte

Alkaline anion-conducting polymer-based CO 2 electrolysis and water electrolysis are among two emerging renewable energy conversion technologies. Their system design and integration offer promise of lower capital cost due to utilization of low-cost catalysts, in contrast to platinum group metal catalysts required for cation-conducting polymer-based devices. However, a critical component, the polymer electrolyte membrane, remains an obstacle hampering system performance and durability. In this study, commercially-available Sustainion® membranes with and without PTFE-reinforcement were investigated to understand previously unreported origins of improved device performance when compared to alternative membrane chemistries. We report critical membrane properties, such as morphology, thermal stability, as well as temperature-, hydration-, and counter-ion dependent ion conductivity. Moveover, the changes in uptake and conductivity of membranes in supporting electrolytes of K 2 CO 3 and KOH investigated as a function of their concentration. Presence of reinforcement and supporting electrolyte type alter the membrane's transport functionality, which could help guide device design for improved performance. In conclusion, the obtained results not only show how Sustainion® properties change with operating environment for CO 2 and water electrolysis applications, but also provide understanding for internal and external factors controlling anion-exhcnage membrane functionality in electrochemical devices.

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

Probing the Effects of Acid Electrolyte Anions on Electrocatalyst Activity and Selectivity for the Oxygen Reduction Reaction

The local microenvironment at the electrode-electrolyte interface plays an important role in electrocatalytic performance. Herein, we investigate the effect of acid electrolyte anion identity on the oxygen reduction reaction (ORR) activity and selectivity of smooth Ag and Pd catalyst thin films. Cyclic voltammetry in perchloric, nitric, sulfuric, phosphoric, hydrochloric, and hydrobromic acid, at pH1, reveals that Ag ORR activity trends as follows: HClO 4 >HNO 3 >H 2 SO 4 >H 3 PO 4 >HCl>>HBr, while Pd ORR activity trends as: HClO 4 >H 2 SO 4 >HNO 3 >H 3 PO 4 >HCl>>HBr. Moreover, rotating-ring-disk-electrode selectivity measurements demonstrate enhanced 4 e - selectivity on both Ag and Pd, by up to 35% H 2 O 2 and 10% H 2 O 2 respectively, in HNO 3 compared to in HClO 4 . Relating physics-based modeling and experimental results, we postulate that ORR performance depends greatly on anion-related phenomena in the double layer, for instance competitive adsorption and non-covalent interactions.

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

Anion and Cation Size Effects on Viscoelasticity and Ion Transport of Imine Vitrimer Electrolytes

Vitrimers are a subclass of covalent adaptable networks where bond exchange occurs without breaking, thereby offering polymer materials with enhanced mechanical strength, thermal stability, and reprocessability compared to conventional electrolytes. Despite recent progress, we lack a complete understanding of the role of ions in controlling the physical and chemical properties of vitrimers. In this work, we study how different salts affect the viscoelasticity, morphology, and ionic conductivity of imine vitrimers. Our results show that addition of salt decreases relaxation times at elevated temperatures due to the catalytic effect of the cations, with smaller cations leading to faster relaxation. However, the activation energy for terminal relaxation increases with smaller cation size. This apparent discrepancy is attributed to the complex interplay among bond exchange kinetics, chain diffusion, and salt dissociation. Anions act as plasticizers by reducing the shear modulus, except lithium bromide. Ionic conductivity increases with larger anions due to smaller salt dissociation energies, whereas the cation type has a minor impact as polymer segmental dynamics dominate ionic transport. Imine-based vitrimers are reprocessable and recyclable, maintaining original mechanical properties and ionic conductivity after recovery. Mixed salt vitrimers exhibited tunable viscoelasticity and ionic conductivity intermediate to the analogous pure salt systems. Altogether, this work highlights the role of salt in the dynamic and conductive properties of imine vitrimers.

Anions↗
DOE OSTI2025

Unraveling Anion-Specific Inhibition and Structural Modulation of Gibbsite Crystallization: Implications for Aluminum Mobility in Natural and Engineered Systems

Gibbsite (α-Al(OH) 3 , sometimes designated as γ-Al(OH) 3 ) plays a crucial role in the chemistry of aluminum in the environment and industry, yet its crystallization behavior under multianionic conditions is not well understood. Here, in this study, we investigate how six common anions─fluoride (F – ), chloride (Cl – ), bromide (Br – ), nitrate (NO 3 – ), sulfate (SO 4 2– ), and phosphate (PO 4 3– )─influence the mineralization, structure, and morphology of gibbsite at room temperature. The results show that PO 4 3– , SO 4 2– , and F – strongly inhibit gibbsite formation, stabilizing amorphous or alternative crystalline phases such as nordstrandite and cryolite. On the contrary, Cl – , Br – , and NO 3 – allow partial to complete crystallization of gibbsite without significant morphological changes. Solid-state 27 Al magic angle spinning nuclear magnetic resonance provides crucial insight into aluminum coordination environments in both crystalline and amorphous phases, distinguishing between octahedral, pentahedral, and tetrahedral Al species. The density functional theory calculations reveal a direct correlation between the Al–X bond strength and the inhibition of crystallization, following the order: PO 4 3– > SO 4 2– > F – > NO 3 – > Cl – > Br – . These findings offer molecular-scale insights into anion-specific effects on aluminum hydroxide nucleation and transformation, improving the understanding of gibbsite formation and aluminum cycling in soils, phosphate retention, contaminant immobilization, and waste treatment strategies in nuclear and industrial settings. These insights can also guide the controlled synthesis of aluminum hydroxide materials with tailored crystallinity and morphology via liquid-assisted methods.

Anions effect↗
DOE OSTI2020

Iodine effective diffusion coefficients through volcanic rock: Influence of iodine speciation and rock geochemistry

Accurate prediction of the subsurface transport of iodine species is important for the assessment of long-term nuclear waste repository performance, as well as monitoring compliance with the Comprehensive Nuclear-Test-Ban Treaty, given that radioiodine decays into radioxenon. However, the transport of iodine through intact geologic media is not well understood, compromising our ability to assess risk associated with radioiodine migration. The current study's goal is to quantify the matrix diffusion of iodine species through saturated volcanic rock, with particular attention paid to the redox environment and potential speciation changes. Here, diffusion experiments were run for iodide through lithophysae-rich lava, lithophysae-poor lava, and welded tuff, whereas iodate diffusion was studied through welded tuff. Iodine transport was compared with a conservative tracer, HDO, and effective diffusion coefficients were calculated. Likely due to a combination of size and anion exclusion effects, iodine species diffused more slowly than the conservative tracer through all rock types tested. Furthermore, oxidation of iodide to iodate was observed in the lithophysae-poor lava, affecting transport. Results provide much needed data for subsurface transport models that predict radioiodine migration from underground sources, and indicate the pressing need for geochemical and redox interactions to be incorporated into these models.

58 GEOSCIENCES↗