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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

The light curve of SN 1987A revisited: constraining production masses of radioactive nuclides

We revisit the evidence for the contribution of the long-lived radioactive nuclides {sup 44}Ti, {sup 55}Fe, {sup 56}Co, {sup 57}Co, and {sup 60}Co to the UVOIR light curve of SN 1987A. We show that the V-band luminosity constitutes a roughly constant fraction of the bolometric luminosity between 900 and 1900 days, and we obtain an approximate bolometric light curve out to 4334 days by scaling the late time V-band data by a constant factor where no bolometric light curve data is available. Considering the five most relevant decay chains starting at {sup 44}Ti, {sup 55}Co, {sup 56}Ni, {sup 57}Ni, and {sup 60}Co, we perform a least squares fit to the constructed composite bolometric light curve. For the nickel isotopes, we obtain best fit values of M({sup 56}Ni) = (7.1 ± 0.3) × 10{sup –2} M {sub ☉} and M({sup 57}Ni) = (4.1 ± 1.8) × 10{sup –3} M {sub ☉}. Our best fit {sup 44}Ti mass is M({sup 44}Ti) = (0.55 ± 0.17) × 10{sup –4} M {sub ☉}, which is in disagreement with the much higher (3.1 ± 0.8) × 10{sup –4} M {sub ☉} recently derived from INTEGRAL observations. The associated uncertainties far exceed the best fit values for {sup 55}Co and {sup 60}Co and, as a result, we only give upper limits on the production masses of M({sup 55}Co) < 7.2 × 10{sup –3} M {sub ☉} and M({sup 60}Co) < 1.7 × 10{sup –4} M {sub ☉}. Furthermore, we find that the leptonic channels in the decay of {sup 57}Co (internal conversion and Auger electrons) are a significant contribution and constitute up to 15.5% of the total luminosity. Consideration of the kinetic energy of these electrons is essential in lowering our best fit nickel isotope production ratio to [{sup 57}Ni/{sup 56}Ni] = 2.5 ± 1.1, which is still somewhat high but is in agreement with gamma-ray observations and model predictions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

{sup 55}Co separation from proton irradiated metallic nickel

{sup 55}Co with > 97% radionuclidic purity 24 hours after end of bombardment (EoB) was produced from the {sup 58}Ni(p,α) reaction using proton irradiations of 16 MeV on natural nickel. Two-hour irradiations with 25 μA on a 254 μm thick nickel foil generate 0.18 ± 0.01 GBq (n = 3) 24 hours after EoB. The separation of cobalt from the target material and other metallic contaminants present at trace levels is accomplished in HCl medium by two rounds of anion exchange chromatography (AG1-X8) using an automated module driven by a peristaltic pump. 80 ± 5 % (n = 3) of the activity generated at EoB is ready for labeling in 0.1 M HCl one hour after the start of separation. Using 99.999% pure Ni, the reactivity (decay corrected to EoB) with the bifunctional chelator (BFC) DOTA was 8.5 GBq/μmol; enough for radiolabeling BFC conjugated biomolecules at a nmol scale with > 90% yield. Using 99.9% pure Ni the reactivity with DOTA and NOTA was 0.19 +/− 0.09 GBq/μmol and 2.9 +/− 1.7 GBq/μmol (n = 2), respectively. Both cobalt complexes showed 100% in vitro stability in PBS and mouse serum over 41 hours at room temperature. MicroPET images of a miniature Derenzo phantom show excellent resolution where rods of 1.5 mm were separated by two times their diameter.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2016

A new insight into neutrino energy loss by electron capture of iron group nuclei in magnetar surfaces

Based on the relativistic mean-field effective interactions theory, and the Lai dong model, we discuss the influences of superstrong magnetic fields (SMFs) on electron Fermi energy, nuclear blinding energy, and single-particle level structure in magnetar surfaces. Using the Shell-Model Monte Carlo method and the Random Phase Approximation theory, we analyze the neutrino energy loss rates (NELRs) by electron capture for iron group nuclei in SMFs. First, when B {sub 12} < 100, we find that the SMFs have a slight influence on the NELRs for most nuclides at relativistic low temperatures (e.g., T {sub 9} = 0.233); nevertheless, the NELRs increase by more than four orders of magnitude at relativistic high temperatures (e.g., T {sub 9} = 15.53). When B {sub 12} > 100, the NELRs decrease by more than three orders of magnitude (e.g., at T {sub 9} = 15.53 for {sup 52–61}Fe, {sup 55–60}Co, and {sup 56–63}Ni). Second, for a certain value of magnetic field and temperature, the NELRs increase by more than four orders of magnitude when ρ{sub 7}⩽10{sup 3}, but as the density increases (i.e., when ρ{sub 7}>10{sup 3}), there is almost no influence on the density of NELRs. For the density around ρ{sub 7}=10{sup 2}, there is an abrupt increase in NELRs when B {sub 12} ≥ 10{sup 3.5}. Such jumps are an indication that the underlying shell structure has changed due to single-particle behavior by SMFs. Finally, we compare our NELRs with those of Fuller et al. (FFN) and Nabi and Klapdor-Kleingrothaus (NKK). For the case without SMFs, one finds that our rates for certain nuclei are close to about five orders of magnitude lower than FFN and NKK at relativistic low temperatures (e.g., T {sub 9} = 1). However, at a relativistic high temperature (e.g., T {sub 9} = 3), our results are in good agreement with NKK, but about one order of magnitude lower than FFN. For the case with SMFs, our NELRs for some iron group nuclei can be about five orders of magnitude higher than those of FFN and NKK. (Note that B {sub 12}, T {sub 9}, and ρ {sub 7} are in units of 10{sup 12} G, 10{sup 9} K, and 10{sup 7} g cm{sup −3}, respectively.)

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Nuclear Data Sheets for A = 54

The 2005 evaluation for A=54 (2006Hu08) has been updated. Detailed experimental nuclear structure data and decay data for all nuclei with mass chain A=54 are presented in this current evaluation. The new data and information are given in following datasets: {sup 54}Ca: {sup 9}Be({sup 76}Ge, X) and Be({sup 55}Sc, p), ({sup 56}Ti, 2p) {sup 54}Sc: {sup 54}Ca β{sup −} decay and {sup 54}Sc IT decay {sup 54}Ti: {sup 54}Sc β{sup −} decay {sup 54}Cr: {sup 54}Mn ε decay, {sup 56}Fe(μ, nupng), and {sup 238}U({sup 64}Ni, Xγ) {sup 54}Mn: {sup 51}V({sup 20}Ne, Xγ), {sup 55}Mn(p, pn), and {sup 56}Fe(μ, nu2ng) {sup 54}Fe: {sup 58}Ni α decay, {sup 9}Be({sup 55}Co, Xγ), {sup 54}Fe(e, e'), {sup 54}Fe(p, p'), and Coulomb Excitation {sup 54}Co: {sup 54}Ni ε decay, {sup 55}Cu εp decay, {sup 28}Si({sup 32}S, αpnγ), {sup 54}Fe(p,n), and {sup 54}Fe({sup 3}He, t) {sup 54}Ni: {sup 54}Ni IT decay, {sup 55}Zn εp decay, {sup 9}Be({sup 55}Ni, Xγ), and {sup 24}Mg({sup 32}S, Xγ) {sup 54}Zn: Ni({sup 58}Ni, X)

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2017

Toward a Four-Electron Redox Quinone Polymer for High Capacity Lithium Ion Storage

Notwithstanding recent advances, current polymeric organic cathode materials have failed to incorporate a high degree of lithium storage in a small molecular framework, resulting in low capacities relative to monomers. This report discloses the development of a lithium salt polymer of dihydroxyanthraquinone (LiDHAQS) capable of storing four Li + per monomer. The combination of storing four Li + per monomer and a low molecular weight monomer results in a capacity of 330 mA h g –1 , a record for this class of material. The additional redox events responsible for added Li + storage occur between 3.0 and 3.6 V versus Li/Li + resulting in an average discharge potential of 2.5 V versus Li/Li + . These metrics combined yield a high energy density of 825 W h kg –1 which is a 55% improvement over commercial lithium cobalt oxide. As a result, the high performance of LiDHAQS makes it a promising material for next generation Li + cathodes.

25 ENERGY STORAGE↗
DOE OSTI2017

Whimper of a Bang: Documenting the Final Days of the Nearby Type Ia Supernova 2011fe

Using the Hubble Space Telescope (HST) and the Large Binocular Telescope, we followed the evolution of the Type Ia supernova (SN Ia) 2011fe for an unprecedented 1840 days past B-band maximum light and over a factor of 7 million in flux. At 1840 days, the 4000–17000 Å quasi-bolometric luminosity is just (420±20) L{sub ⊙}. By measuring the late-time quasi-bolometric light curve, we present the first confident detection of {sup 57}Co decay in a SN Ia light curve and estimate a mass ratio of log({sup 57}Co/{sup 56}Co)=−1.59{sub −0.07}{sup +0.06}. We do not have a clean detection of {sup 55}Fe, but find a limit of {sup 55}Fe/{sup 57}Co<0.22 with 99% confidence. These abundance ratios provide unique constraints on the progenitor system because the central density of the exploding white dwarf(s) dictates these nucleosynthetic yields. The observed ratios strongly prefer the lower central densities of double-degenerate models ({sup 55}Fe/{sup 57}Co=0.27) over the higher central densities of near-Chandrasekhar-mass single-degenerate models ({sup 55}Fe/{sup 57}Co=0.68). However, additional theoretical studies predicting isotopic yields from a broader range of progenitor systems are motivated by these unique observations. We will continue to observe SN 2011fe for another ∼600 days with HST and possibly beyond.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Sustainable recovery of critical metals from spent lithium-ion batteries through gluconic acid-based bioleaching: Techno-economic analysis, life cycle assessment and process optimization

Recycling spent lithium-ion batteries (LIB) could potentially bridge the ever increasing supply and demand gap for critical metals and simultaneously facilitate the management of hazardous battery waste. This study investigated the optimization of gluconic acid-based bioleaching technology through design of experiments (DOE), combined with techno-economic analysis (TEA), and life cycle assessment (LCA) with the aim of maximizing the net present value (NPV) and minimizing global warming impacts of the process. Biolixiviant containing predominantly gluconic acid produced by the genetically engineered (ΔpstS, P 112 :mgdh) Gluconobacter oxydans B58 through fermentation using non-recyclable paper as a growth substrate was used for the LIB leaching. At optimal bioleaching conditions of gluconic acid (160 mM), leaching time (2.5 h), reducing agent FeSO 4 to metal, i.e., cobalt (Co), nickel (Ni) and manganese (Mn), mole ratio (0.88), temperature (55 °C) and pulp density (2.5 %), the leaching efficiency was 87 % 72 %, 94 %, and 88 % for Co, Ni, Mn and lithium (Li), respectively. TEA analysis confirmed that bioleaching plant with an annual black mass processing capacity of 10,000 metric tons and plant life of 30 years would be economically viable with an NPV and profit margin of $136 million and 11 %, respectively. The predicted carbon footprint of gluconic acid-based bioleaching for recovering 1 kg of Co (13.2 kg of CO 2 eq.) is lower compared to that of most state-of-the-art leaching technologies. Moreover, gluconic acid-based bioleaching effectively recovered target metals when tested for different black mass chemistries.

Bioleaching↗
DOE OSTI2019

Analysis of Material Properties of Aged Rigid Polyurethane Foam

Polyurethane foams are organic materials which can be classified as mechanically rigid or flexible. They are chemically inert, relatively unaffected by the presence of water (cracking, swelling, absorption), and can be manufactured in densities from 3-40 lb/ft 3 . In addition, polyurethane foams have exceptional mechanical and thermal properties, which support use of polyurethane foams in the 9977 shipping packages. These packages are designed for shipment of special nuclear material and are approved for storage in the K-area complex (KAC) at Savannah River Site. Through the analysis of conditioned foams, a service life ofFR-3700 can be estimated for the storage of the 9977 packages. Thus, considering anticipated temperatures of the 9977 packages in the KAC, FR-3700 was conditioned at 160°F, 185°F, 215°F, 250°F, and 160°F with 50% relative humidity, which remains within the service temperature of-320°F - 250°F of the FR-3700 foam in the 9977 packages. Prior studies have analyzed foams after 7, 20, and 30 months of conditioning with the current study analyzing foams up to 55 months of conditioning. Considering the limited information on the effects of radiation on FR-3700, samples were irradiated with a cobalt-60 source at a high and low dose rate of 90.9 krad/hr and 16.67 krad/hr, respectively, to examine the effects of irradiation and dose rate on thermal properties. It was found that foams conditioned up to 55 months had comparable heat capacity values to FR-3700, with a slight increase due to humidity. Results suggest that fire additives began decomposing at higher conditioning temperatures, reducing the average percent mass loss. Overall, irradiation and humidity had minimal effects on thermal properties of FR-3700.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Sustainable bioleaching of lithium-ion batteries for critical metal recovery: Process optimization through design of experiments and thermodynamic modeling

Recycling spent lithium-ion batteries (LIBs) could alleviate supply risks for critical metals and be less harmful to the environment compared to new production of metals from mining. Developing a cost-effective LIB bioleaching process could be a promising alternative to traditional energy-intensive recycling technologies. Here, this study aimed to optimize bioleaching conditions for maximum economic competitiveness through design of experiments using iterative response surface methodology (RSM), assisted by thermodynamic modeling. The optimal condition was identified as 2.5% pulp density in 75 mM gluconic acid biolixiviant at 55°C for 30 h which could recover 57%–84% of nickel, 71%–86% of cobalt, and 100% of lithium and manganese, yielding a 17%–26% net profit margin. The recommended pulp density and acid concentrations, together with the observed metal solubilization, were supported by thermodynamic modeling predictions. Our study demonstrated that combining RSM with thermodynamic simulations could be a powerful tool for optimizing bioleaching conditions.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Immunotoxicological and neurotoxicological profile of health effects following subacute exposure to geogenic dust from sand dunes at the Nellis Dunes Recreation Area, Las Vegas, NV

Exposure to geogenic particulate matter (PM) comprised of mineral particles has been linked to human health effects. However, very little data exist on health effects associated with geogenic dust exposure in natural settings. Therefore, we characterized particulate matter size, metal chemistry, and health effects of dust collected from the Nellis Dunes Recreation Area (NDRA), a popular off-road vehicle area located near Las Vegas, NV. Adult female B6C3F1 mice were exposed to several concentrations of mineral dust collected from active and vegetated sand dunes in NDRA. Dust samples (median diameter: 4.4 μm) were suspended in phosphate-buffered saline and delivered at concentrations ranging from 0.01 to 100 mg dust/kg body weight by oropharyngeal aspiration. ICP-MS analyses of total dissolution of the dust resulted in aluminum (55,090 μg/g), vanadium (70 μg/g), chromium (33 μg/g), manganese (511 μg/g), iron (21,600 μg/g), cobalt (9.4 μg/g), copper (69 μg/g), zinc (79 μg/g), arsenic (62 μg/g), strontium (620 μg/g), cesium (13 μg/g), lead 25 μg/g) and uranium (4.7 μg/g). Arsenic was present only as As(V). Mice received four exposures, once/week over 28-days to mimic a month of weekend exposures. Descriptive and functional assays to assess immunotoxicity and neurotoxicity were performed 24 h after the final exposure. The primary observation was that 0.1 to 100 mg/kg of this sand dune derived dust dose-responsively reduced antigen-specific IgM antibody responses, suggesting that dust from this area of NDRA may present a potential health risk. - Graphical abstract: During periods of heavy wind erosion, dense dust clouds of locally emitted geogenic dust enrobe the central Nellis Dune Recreation Area dunes. - Highlights: • Toxicological effects were characterized specific to geogenic dust exposure from a recreational sand dune site in Nevada. • The geogenic dust is a mixture of many metals and crystalline silica. • Exposure to geogenic dust dose-responsively decreased IgM antibody responses in a mouse model.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Impact of Electrolyte Additives on the Lifetime of High Voltage NMC Lithium-Ion Pouch Cells

This work involves improving the lifetime of lithium-ion cells during high voltage cycling using electrolyte additives. Three generations of electrolyte additives were investigated and screened in NMC442/graphite pouch cells using a 24 h voltage-hold protocol at 40 degrees C to accelerate oxidative reactions occurring at 4.4 V. Once promising additives and combinations were identified, they were then tested in cobalt-free NMC640/graphite cells for long-term cycling to upper cutoff voltages of 4.3, 4.4, and 4.5 V at temperatures of 20, 40, and 55 degrees C. Degradation mechanisms were probed using dV/dQ analysis, micro-X-ray fluorescence spectroscopy, and electrochemical impedance spectroscopy. The primary failure mode of cells held at high voltages is due to increase in cell impedance, which is correlated to the dissolution of transition metals, specifically manganese, originating from the positive electrode. We believe this dissolution is presumably due to the formation of a high impedance rock salt surface layer on the NMC positive electrode particles. Such deleterious outcomes can be limited by selecting an appropriate electrolyte additive package. It is hoped that this paper can provide a starting point for developing NMC Li-ion cells that can operate to voltages as high as 4.4 V and still display long lifetimes.

Azam, Saad↗
DOE OSTI2014

Terbium induced glassy magnetism in La,Ca-based cobaltites

The La{sub 0.8–x}Tb{sub x}Ca{sub 0.2}CoO{sub 3} cobaltites of orthoperovskite Pbnm structure were investigated by the X-ray and neutron diffraction, specific heat, and magnetization measurements. The terbium doping has two important effects, it increases the size disorder on perovskite A-sites and influences the magnetic properties due to large Ising-type moments (∼8.9 Bohr magnetons per Tb). The compounds show a bulk magnetic moment below T{sub C} = 82 K, 53 K, and 30 K for x = 0.1, 0.2, and 0.3, respectively. The neutron diffraction evidences a long-range ferromagnetic arrangement of cobalt moments, combined below ∼20 K with ordering of terbium moments in a canted arrangement. A homogeneous magnetic phase is proved for the x = 0.1 sample, while x = 0.2 and 0.3 are in an intrinsically non-homogeneous magnetic state with long-range ordering only comprising 55% and 30% of the sample volumes. The ac susceptibility experiments prove a glassy character of the terbium doped samples and provide arguments for the short-range ordering above T{sub C} and wide distribution of relaxation times.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

NiCo-lead zirconium titanate-NiCo trilayered magnetoelectric composites prepared by electroless deposition

The NiCo layers with various Ni/Co atomic ratio have been successfully electroless deposited on PZT layers by varying the bath composition. As the cobalt atomic ratio in the deposited layer increases from 17.2 to 54.8 wt%, the magnetostrictive coefficient decreases. The magnetoelectric effect depends strongly on the magnetostrictive properties of magnetostrictive phase. The magnetoelectric coefficient of NiCo/PZT/NiCo trilayers increases with Ni/Co atomic ratio of the deposited NiCo layers increasing from 45:55 to 83:17. A maximum ME voltage coefficient of α{sub E,31} = 2.8 V ⋅ cm{sup −1} ⋅ Oe{sup −1} is obtained at a frequency of about 88 kHz, which makes these trilayers suitable for applications in actuators, transducers and sensors.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy

Abstract Structural and interfacial instability of the LiCoO 2 cathode under a voltage exceeding 4.5 V (vs Li/Li + ) severely hinders its practical applications for high‐energy‐density lithium batteries. Herein, a modified electrolyte with nitriles (suberonitrile or 1,3,6‐hexanetricarbonitrile) and fluoroethylene carbonate (FEC) coadditives is demonstrated to form an ultrathin and uniform interface layer on LiCoO 2 cathode under a synergetic effect. As such, LiCoO 2 /Li cells display excellent cyclability at a cutoff voltage of 4.6 V with a capacity retention over 72% after 300 cycles and 60% after 200 cycles at 30 and 55 °C, respectively, even achieving operation at a high current rate (10 C) upon 500 cycles as compared to the controls with fast‐falling capacity to zero. Furthermore, an adsorption‐coordination mechanism between nitriles and cobalt and synergetic effect of coadditives are explored by the alliance of spectroscopic analysis and theoretical calculations. The contributed lone‐pairs on the N 2p orbital of nitriles in coordination lowers the real oxidation state of Co 3+/4+ so that it decreases its catalysis on electrolytes, and the synergy from nitrile‐derived species regulates FEC to form an LiF‐containing electron‐insulated interface layer. This work shares a new insight to nitriles with the synergy of coadditives and paves a way to refine (ultra)high‐voltage LiCoO 2 cathode for high‐energy‐density energy storages.

Yang, Xuerui↗
DOE OSTI2019

Transition metal-doped 3C-SiC as a promising material for intermediate band solar cells

In this report the un-surveyed domain of silicon-based intermediate band solar cell (IBSC) has been studied. Intermediate band (IB) has been created in 3C-SiC through substitution of cobalt (Co) atoms within super cell structures as a consequence of interaction between the crystalline potential and spin interaction with d orbitals of Co. The band structure, density of state and absorption coefficient of the new material have been extracted. Large band gap of 3C-SiC along with the proper selection of the guest Co atoms provides both high conversion efficiency and also, the possibility to reach the theoretical optimal band gap for photovoltaic applications. However, we demonstrated that a metallic narrow IB is formed whiten the forbidden band energy of 3C-SiC when Co atoms are located inside that. The maximum conversion efficiencies near 60% and 55% are obtained under AM1.5 and AM0 spectra, respectively. Our theoretical results provide a possible way to design high efficiency solar cell based on silicon carbide.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

PET Imaging of the Neurotensin Targeting Peptide NOTA-NT-20.3 Using Cobalt-55, Copper-64 and Gallium-68

Introduction: Neurotensin receptor 1 (NTSR1) is an emerging target for imaging and therapy of many types of cancer. Nuclear imaging of NTSR1 allows for noninvasive assessment of the receptor levels of NTSR1 on the primary tumor, as well as potential metastases. This work focuses on a the neurotensin peptide analogue NT-20.3 conjugated to the chelator NOTA for radiolabeling for use in noninvasive positron emission tomography (PET). NOTA-NT-20.3 was radiolabeled with gallium-68, copper-64, and cobalt-55 to determine the effect that modification of the radiometal has on imaging and potential therapeutic properties of NOTA-NT-20.3. Methods: In vitro assays investigating cell uptake and subcellular localization of the radiolabeled peptides were performed using human colorectal adenocarcinoma HT29 cells. In vivo PET/CT imaging was used to determine the distribution and clearance of the peptide in mice bearing NTSR1 expressing HT29 tumors. Results: Cell uptake studies showed that the highest uptake was obtained with [ 55 Co] Co-NOTA-NT-20.3 (18.70 ± 1.30%ID/mg), followed by [ 64 Cu] Cu-NOTA-NT-20.3 (15.46 ± 0.91%ID/mg), and lastly [ 68 Ga] Ga-NOTA-NT-20.3 (10.94 ± 0.46%ID/mg) (p < 0.001). Subcellular distribution was similar across the three constructs, with the membranous fraction containing the highest amount of radioactivity. In vivo PET/CT imaging of the three constructs revealed similar distribution and tumor uptake at the 1 h imaging timepoint. Tumor uptake was receptor-specific and blockable by co-injection of non-radiolabeled NOTA-NT-20.3. SUV ratios of tumor to heart at the 24 h imaging timepoint show that [ 55 Co] Co-NOTA-NT-20.3 (20.28 ± 3.04) outperformed [ 64 Cu] Cu-NOTA-NT-20.3 (6.52 ± 1.97). In conclusion, our studies show that enhanced cell uptake and increasing tumor to blood ratios over time displayed the superiority of [ 55 Co] Co-NOTA-NT-20.3 over [ 68 Ga] Ga-NOTA-NT-20.3 and [ 64 Cu] Cu-NOTA-NT-20.3 for the targeting of NTSR1.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Chlorocobaltate-Enabled Selective Separation of CoCl 2 from Mixed Chloride and Nitrate Salts of Mn, Co, and Ni

Described here is the effect of anionic metalates─chlorocobaltate and nitratocobaltate─on the heat-driven separation of the critical element cobalt from potentially competing transition metal salts. Resins bearing the hexadentate glycolamide receptor L (PS-L) exhibit sorption capacities, Q = 1.33 mmol/g for CoCl 2 and Q = 0.66 mmol/g for Co(NO 3 ) 2 , as inferred from sorption isotherm studies. This trend runs counter to the typical Hofmeister series for anion selectivity. Ion chromatographic analysis of a mixed CoCl 2 /Co(NO 3 ) 2 solution revealed an increase in chloride content from 55 mol % to 90 mol % after a single thermally driven catch-and-release cycle. This chloride-selective behavior was recapitulated in a mixed-metal cation, mixed-anion system containing the chloride and nitrate salts of Mn(II), Co(II), and Ni(II) at near-equimolar concentrations. PS-L also displayed enhanced selectivity for Co using this mixed stock solution as observed by ICP-OES. In contrast, for a nitrate-only solution containing Mn(II), Co(II), and Ni(II), PS-L showed increased affinity for Mn, with its proportion rising from 36.6 mol % to 58.1% after a single catch-and-release cycle. Density functional theory calculations support the suggestion that the enhanced uptake of Co(II) in chloride-rich media arises from the high thermodynamic stability of [CoCl 4 ] 2– , which facilitates its outer-sphere coordination to cationic resin-bound cobalt species. Single crystal X-ray crystallographic analyzes of L•MCl 2 (M = Mn, Co, Ni) and L•M(NO 3 ) 2 (M = Mn, Co) confirmed metal complexation by L in the solid state and the concomitant formation of metalate counteranions. Here, the present study highlights a relatively simple approach for separating cobalt from its transition metal congeners.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗