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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 OSTI2022

Porous Liquids as Electrolyte: A Case Study of Li + and Mg 2+ Ion Transport in Crown Ether-Based Type-II Porous Liquids

Here, we demonstrate crown ether (CE)-based type II porous liquid (PL) electrolytes in which CEs provide internal porosity and are capable of coordinating with Li + and Mg 2+ ions. We investigated the physicochemical properties of the PL electro-lytes with different functional groups and cavity sizes. Among the electrolytes studied, the 12-crown-4 (12C4)-based PL electrolyte exhibited the most enhanced ionic conductivity due to size match between the CE cavity and the Li + ion. Nu-clear magnetic resonance and Fourier transform infrared analyses revealed that addition of CEs reduces the Li + ion–solvent interaction, resulting in the formation of Li-CE complexes. The simulation study clearly showed that the solvated Li + and Mg 2+ ions form complexes with 12C4. The strategy described here using CE-based PLs should be applicable to the design versatile electrolytes for various metal-ion batteries.

Shin, Sun Hae Ra↗
DOE OSTI2024

Constructing Crown Ether-Based Supramolecular Adhesives with Ambient-Temperature Applicable and Durable Adhesion

Supramolecular adhesives are attracting considerable attentions owing to their dynamic and reversible bonding, while the complex curing conditions and poor performance under extreme conditions severely restrict their applicability. Herein, a series of tetra-crown ether-terminated polyethylene glycol (TCE-PEG) adhesives are presented in which plenty of supramolecular interactions, including Van der Waals, hydrogen bonding, π–π staking, metal coordination, and electrostatic ones, provide strong adhesion on multiple types of substrates. Highly relevant for practical applications, ultra-strong adhesivity of TCE-PEG can be achieved without requiring additional ultraviolet radiation, heat, or chemical treatment at ambient temperature. It also exhibits durable adhesive behavior, excellent underwater stability, and low-temperature tolerance. Especially, by incorporating ionic polymer fragments of polyethyleneimine hydrochloride, additional hydrogen bonding between secondary amines and crown ether rings can be induced to enhance the lap-shear strength to 7.21 MPa due to the formation of supramolecular cross-linked network. Finally, this work pioneers a rather unique supramolecular approach for easily formed, ultra-strong crown-ether-based adhesives bearing great potential for applications in critical environments of limited heat source and unallowed solvent usage.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Development of Crown Ether-Functionalized Polymeric Sorbents for Lithium-Ion Capture

The purpose of this Cooperative Research and Development Agreement (CRADA) was to develop and demonstrate new synthetic strategies for fabricating lithium-selective polymeric adsorbents by covalently incorporating crown ether functionalities into durable, processable support materials. These advanced sorbents are designed to selectively extract lithium ions (Li⁺) from dilute aqueous sources such as brine, seawater, industrial wastewater, and battery recycling streams.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

Irvin, Jennifer A.↗
NASA NTRS1992

12-Crown-4 Ether Improves Rechargeable Lithium Cells

Experiments show addition of 12-crown-4 ether (12Cr4) to thin film of polyethylene oxide (PEO) and LiBF4 reduces charge-transfer resistance of film and enhances performance of electrochemical cell in which film is electrolyte, anode is lithium, and cathode is LixCoO2. By increasing conductivity of the electrolyte, 12Cr4 reduces polarization loss; enabling cell to sustain higher current. Result is new type of rechargeable lithium cell.

Nagasubramanian, Ganesan↗
NASA NTRS1992

Effects of 12-crown-4 ether on the electrochemical performance of CoO2 and TiS2 cathodes in Li polymer electrolyte cells

The effect of adding 12-crown-4 ether (12Cr4) to the polyethylene oxide (PEO) electrolyte on the electrochemical properties of cells with Li(x)CoO2 or TiS2 as the cathode was investigated. The polymer electrolyte films were: (1) PEO, LiBF4; (2) PEO, LiBF4 with 12Cr4; (3) Li(x)CoO2, PEO, and LiBF4; and (4) Li(x)CoO2, PEO, LiBF4, and 12Cr4. It was found that, although 12Cr4 improved the cell performance over cells without 12Cr4 in the shallow c/d cycles (cyclic voltammetric behavior), it did not seem to prolong the active life of the cell. The cells with CoO2 as the cathode failed after a few c/d cycles, while similar cells with TiS2 did not fail even after 12 c/d cycles. The probable cause of failure in the case of CoO2 is ascribed to the instability of the CoO2 cathode.

Nagasubramanian, G.↗
NASA NTRS1990

Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

Nagasubramanian, G.↗
NASA NTRS1992

Secondary Li battery incorporating 12-Crown-4 ether

A rechargeable lithium battery which utilizes a polyethylene oxide (PEO) solid polymeric electrolyte complexed with a lithium salt is disclosed. The conductivity is increased an order of magnitude and interfacial charge transfer resistance is substantially decreased by incorporating a minor amount of 12-Crown-4 ether in the PEO-lithium salt solid electrolyte film. Batteries containing the improved electrolyte permit operation at a lower temperature with improved efficiency.

Nagasubramanian, Ganesan↗
DOE OSTI2024

Supramolecular Complexation-Enhanced CO 2 Chemisorption in Amine-Derived Sorbents

A supramolecular complexation approach is developed to improve the CO 2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. Here, the reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO 2 capacity and diminished energy consumption in sorbent regeneration are achieved.

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

Alkali Metal Cation Effects for Rapid C–H Activation by Iron(0) Complexes

C–H oxidative addition is a key reaction in organometallic catalysis, motivating efforts to accelerate it. Here, we examine an anionic beta-diketiminate-supported iron(0) species that was previously observed to activate C-H bonds with Na(15-crown-5), but not with K(18-crown-6) or Rb(18-crown-6). Though crown ethers are usually seen as beneficial due to their ability to solubilize alkali metal cations, we observe that removing the crown ether leads to rapid and complete oxidative addition of the C-H bond even by K, Rb, and Cs. The products are iron(II) phenyl hydride complexes that exist as dimers bridged by the alkali metals. Neutron crystallography of the cesium complex verifies the presence and location of the bridging hydrides. It is likely that the crown-free alkali metal cations have greater Lewis acidity that enables them to facilitate oxidative addition of the C-H bond. This system gives insight on how to control the rate and favorability of C-H activation through manipulation of the countercation.

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

An Application of Molecular Recognition for the Efficient Removal of Cesium from Hanford Nuclear Waste by Modular Solvent Extraction

In this work, experimental results leading to flowsheet design are presented showing how a calixarene-crown ether based solvent-extraction process can meet the challenge of cesium removal from nuclear tank wastes stored at the US Department of Energy Hanford site. Cleanup of legacy Cold War nuclear waste stored in underground tanks represents one of the greatest environmental challenges facing the US Department of Energy in terms of risk, cost, and effectiveness of applicable science and technology. Planning for the cleanup at the Hanford Site calls for the removal of the radioactive fission product 137Cs from its alkaline salt waste, including the use of modular processes that can be deployed near the tank farms. To meet the resulting need for extremely high selectivity, the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) process employing a calix[4]arene-crown ether in modified kerosene has been adapted to remove sub-millimolar cesium in competition with molar sodium and potassium in a high-nitrate alkaline matrix. Potassium loading in the solvent was determined in extraction, scrubbing, and stripping, leading to an empirical model closely approximating cesium distribution ratios for a variety of Hanford waste types. Process chemistry has been developed based on this molecular-recognition approach, focusing on the competitive effect of potassium loading and the mitigating process modifications needed, including extending the scrub section. The result is a modular flowsheet design that can achieve cesium decontamination factors well in excess of 15,000 even for the worst-case Hanford waste.

Williams, Neil [ORNL] (ORCID:000000023159226X)↗
DOE OSTI2022

Selective Removal of Barium and Hardness Ions from Brackish Water with Chemically Enhanced Electrodialysis

The use of a nonconventional water resource for energy and industrial applications often requires extraction of low-level undesirable ions from matrices of benign dominant ions. In this study, the selective extraction of Ba 2+ and Mg 2+ from synthetic brine solutions was evaluated using strong acid cation-exchange membranes modified with the surface deposition of macrocyclic molecules including crown ethers and calixarenes. Compared to the bare membrane, vinylbenzo-18-crown-6 (VB18C6) and calix[4]arene-amended membranes showed increased selectivity for Ba 2+ and Mg 2+ with respect to the dominant ion (Na + ) by up to fourfolds, with the calix[4]arene-modified membrane achieving more selective separation than VB18C6. Optimal selectivity was achieved at a moderate-to-high current density (3.1–6.3 mA/cm 2 ), which was attributed to the alleviation of transport limitation in the boundary layer by the surface modification. Amendment of a calix[4]arene derivative with a crown-6 “boot strap” and two carboxylic groups resulted in reduced selectivity due to the formation of strong complexes with divalent ions. Furthermore, these results show that surface deposition of ion sequestrants can be a versatile approach to improve the membrane’s selectivity; however, the performance is sensitive to feed water salinity, current loading, and the macrocycle-ion chemistry, where there is a trade-off between ion affinity and mobility.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Enhancing durability of polymer electrolyte membrane using cation size selective agents

Radical species generated during proton exchange membrane fuel cell operation considerably limit the achievable durability, particularly for heavy-duty vehicle applications. A promising solution to the problem is the incorporation of radical scavenger additives such as cerium which mitigates chemical attacks on the membrane. However, these additives migrate during fuel cell operation causing a loss in durability and performance due to detrimental interaction with various components of the fuel cell. Here, we study cation size selective agents as a means to immobilize cerium within perfluorosulfonic acid (PFSA) membranes. We synthesized an organometallic complex of cerium with 15-Crown-5 and investigated the effectiveness of this complex to immobilize cerium. Over 300% increase in cerium retention and an 80% increase in chemical durability were observed owing to the stabilization effect of crown ethers on cerium. Migration under a potential gradient can be eliminated while the complex also contributes to the enhancement in cerium radical scavenging activity. In conclusion, current challenges with the proposed solution are highlighted and future work is discussed.

25 ENERGY STORAGE↗
DOE OSTI2025

Nanofiltration Membranes for Li + /Mg 2+ Separation: Materials and Mechanisms

Nanofiltration (NF) membranes have garnered significant interest for Li + /Mg 2+ separation, a crucial step in lithium extraction from brines. The state-of-the-art commercial LiNE-XD membrane exhibits a Li + /Mg 2+ separation factor (SF Li/Mg ) of 42 at pH 3.3, due to the positive charges on the membrane surface and its strong size-sieving ability. Membranes with higher separation factors at a broad pH range are being pursued to improve separation efficiency. This work aims to provide a timely and comprehensive assessment of advanced NF membranes with superior Li + /Mg 2+ separation properties, as well as their structure and property relationships for designing next-generation membranes. We describe transport mechanisms for ions in NF membranes and discuss governing parameters and models employed to quantify the Li + /Mg 2+ separation. High-performance membrane materials are exhaustively introduced, including commercial and modified polyamides, two-dimensional materials, metal–organic frameworks, crown ethers, and their blends. Finally, we critically compare these membranes in an upper bound plot and highlight the opportunities and challenges of NF membranes for practical Li + /Mg 2+ separations.

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

Evaluation of chromatographic resins for high efficacy separation of radium from chemical analogues

The separation of Radium (Ra) from interfering chemical analogues is of major importance for both the accurate measurement of Ra-226 in environmental samples and the preparation of radium targets destined for medical isotope production. The adsorption behavior of Ra, Barium (Ba), and Strontium (Sr) was investigated on multiple crown-ether-based proprietary extraction chromatographic resins developed by TrisKem Int. Among these, the TK101 resin, characterized by a novel room-temperature ionic liquid (RTIL) dual extractant–solvent system, demonstrated enhanced affinity and selectivity, particularly at low acid concentrations, achieving a D w of 3477 ± 73 for Ra in 0.04 M HNO₃, whereas the maximum Ra D w obtained with the traditional Sr resin in 8 M HNO 3 was only 12.33 ± 0.4. In 0.04 M HNO 3 , a Ra distribution ratio (D w ) of 776 was achieved within 1 min, indicating rapid uptake kinetics. The adsorption capacities were estimated at 19.6 ± 0.1 mg/g for Ba and 12.0 ± 0.2 mg/g for Sr. However, competing alkali metals significantly reduced alkaline earth metal uptake, indicating that the TK101 resin is best suited for radium purification following a preconcentration step to minimize matrix effects in high salinity samples. Dynamic column studies confirmed the strong chromatographic performance of the TK101 resin, with no significant Ba or Sr breakthrough in the Ra fraction and a Ra recovery of 87 ± 2.8%. These results demonstrate the potential of the TK101 resin for selective radium separation in analytical and radiochemical applications.

and nuclear chemistry↗
NASA NTRS2005

Homopolyrotaxanes and Homopolyrotaxane Networks of PEO

In order to identify the optimum size of macrocrown ether for threading, we first investigated the size and shape of simple crown ethers in the melt at 373 K, and their extent of threading with PEO in the melt using coarse-grained Monte Carlo simulations on the 2nnd (second nearest neighbor diamond) lattice, which is a high coordination lattice whose coarse-grained chains can be reverse mapped into fully atomistic models in continuous space.

Pugh, Coleen↗
DOE OSTI2022

Terminal and Super‐Basic Parent Imides of Hafnium

Abstract A dinuclear hafnium complex containing the parent imido ligand [(PN)(PNC)Hf=NH{μ 2 ‐K}] 2 ( 2 ) (PN − =(N‐(2‐P i Pr 2 ‐4‐methylphenyl)‐2,4,6‐Me 3 C 6 H 2 ; PNC 2− =(N‐(2‐P i Pr 2 ‐4‐methylphenyl)‐2,4,6‐CH 2 Me 2 C 6 H 2 ), was prepared by reduction of the bisazide trans‐[(PN) 2 Hf(N 3 ) 2 ] ( 1 ) with two equiv of KC 8 . Encapsulation of K + in 2 with crown‐ether or cryptand affords the first discrete salt [K(encap)][(PN)(PNC)Hf≡NH] (encap=18‐crown‐6(THF) 2 , 3 ; 2,2,2‐Kryptofix, 4 ), featuring a terminal parent imide and possessing some of the shortest Hf−N bond lengths known to date. DFT calculations revealed formation of 2 to proceed via an extremely basic monomeric nitrido, [(PN) 2 Hf≡N] − ( A ), having a computed p K BH+ of ∼57 followed by heterolytic splitting of an inert 1,2‐CH bond of a benzylic methyl group across the Hf≡N triple bond in A . An electronic structure analysis reveals A to possess a covalent Hf≡N triple bond and of super‐basic character. We also showcase reactivity of the Hf≡NH bond with various electrophiles.

Chemistry↗
DOE OSTI2022

Carbodiimide‐Induced Formation of Transient Polyether Cages**

Abstract The use of “fuel” compounds to drive chemical systems out of equilibrium is currently of interest because of the potential for temporally controlled, responsive behavior. We have recently shown that transiently formed crown ethers exhibit counterintuitive templation effects when generated in the presence of alkali metal cations: “matched” cations, such as K + with an 18‐crown‐6 analogue, suppress the formation of the macrocycles (negative templation). In this work, we describe two macrocyclic diacids that, on treatment with carbodiimides, give transient macrobicyclic cages analogous to polyether cages. Negative templation effects are observed for the smaller cage when generated in the presence of K + and Na + , but there is a weak, but reproducible, positive templation effect in the presence of Li + . The larger cage behaves similarly in the presence of Li + , K + , Rb + , and Cs + , but differently with Na + , which appears to bind to both the cage and the initial macrocycle.

Hossain, Mohammad Mosharraf↗