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At least 163 records · Page 9

A geologic assessment of potential lunar ores

Although bulk lunar soil is not a suitable feedstock for extracting metals, certain minerals such as anorthite and ilmenite can be separated and concentrated. These minerals can be considered as potential ores of aluminum, silicon, titanium, andiron. A separation and metal extraction plant could also extract large amounts of oxygen and perhaps hydrogen from these minerals. Anorthie containing 19 percent aluminum and 20 percent silicon can be concentrated from some highland soils where it is present in amounts up to 60 percent. Ilmenite containing 32 percent titanium and 37 percent iron can be concentrated from some mare soils where it is present in amounts up to 10 percent. The ideal mining site would be located at the boundary between a high-titanium mare and a high-aluminum highlands. Such area may exist around the rims of some eastern maria, particularly Tranquilitatis. A location on Earth with raw materials as described above would be considered an economically valuable ore deposit if conventional terrestrial resources were not available.

Mckay, D. S.↗

Spectral Addressability in a Modular Two Qubit System

The combination of structural precision and reproducibility of synthetic chemistry is perfectly suited for the creation of chemical qubits, the core units of a quantum information science (QIS) system. By exploiting the atomistic control inherent to synthetic chemistry, we address a fundamental question of how the spin–spin distance between two qubits impacts electronic spin coherence. To achieve this goal, in this study we designed a series of molecules featuring two spectrally distinct qubits, an early transition metal, Ti 3+ , and a late transition metal, Cu 2+ with increasing separation between the two metals. The spectral separation between the two metals enables us to probe each metal individually in the bimetallic species and compare it with monometallic control samples. Coherence times found to be governed by the distance to nuclear spins on the other qubit’s ligand framework. This finding offers guidance for the design of spectrally addressable molecular qubits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.

Zhou, Qiongyu↗

Metal–Organic Frameworks for C6 Alkane Separation

The separation of alkane isomers is an important yet challenging process in the petrochemical industry. Being a crucial step to produce premium gasoline components as well as optimum ethylene feed, the current industrial separation by distillation is extremely energy intensive. Adsorptive separation based on zeolite is limited by insufficient adsorption capacity. Metal-organic frameworks (MOFs) hold enormous promise as alternative adsorbents due to their diverse structural tunability and exceptional porosity. Precise control of their pore geometry/dimensions has led to superior performance. In this minireview, we highlight the recent progresses in developing MOFs for the separation of C6 alkane isomers. Representative MOFs are reviewed based on their separation mechanisms. Emphasis is put on the material design rationale for achieving optimal separation capability. Lastly, we briefly discuss the existing challenges, possible solutions, and future directions of this important field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating metal-centered dimerization of a lanthanide chaperone protein for separation of light lanthanides

Elucidating details of biology’s selective uptake and trafficking of rare earth elements, particularly the lanthanides, has the potential to inspire sustainable biomolecular separations of these essential metals for myriad modern technologies. Here, we biochemically and structurally characterize Methylobacterium (Methylorubrum) extorquens LanD, a periplasmic protein from a bacterial gene cluster for lanthanide uptake. This protein provides only four ligands at its surface-exposed lanthanide-binding site, allowing for metal-centered protein dimerization that favors the largest lanthanide, La III . However, the monomer prefers Nd III and Sm III , which are disfavored lanthanides for cellular utilization. Structure-guided mutagenesis of a metal-ligand and an outer-sphere residue weakens metal binding to the LanD monomer and enhances dimerization for Pr III and Nd III by 100-fold. Selective dimerization enriches high-value Pr III and Nd III relative to low-value La III and Ce III in an all-aqueous process, achieving higher separation factors than lanmodulins and comparable or better separation factors than common industrial extractants. Finally, we show that LanD interacts with lanmodulin (LanM), a previously characterized periplasmic protein that shares LanD’s preference for Nd III and Sm III . Our results suggest that LanD’s unusual metal-binding site transfers less-desirable lanthanides to LanM to siphon them away from the pathway for cytosolic import. The properties of LanD show how relatively weak chelators can achieve high selectivity, and they form the basis for the design of protein dimers for separation of adjacent lanthanide pairs and other metal ions.

lanthanide biochemistry↗

In Situ Scattering Studies of Crystallization Kinetics in a Phase-Separated Zr–Cu–Fe–Al Bulk Metallic Glass

In this work, thermal stability and the crystallization kinetics of a phase-separated Zr-Cu-Fe-Al bulk metallic glass were investigated using in situ high-energy synchrotron X-ray and neutron diffraction, as well as small-angle synchrotron X-ray scattering. It was revealed that this glass with excellent glass-forming ability possesses a two-step crystallization behavior. The crystalline products and their evolution sequence are more complicated than a homogeneous Zr-Cu-Al glass with average glass-forming ability. The experimental results indicate that a finely distributed nanometer-sized cubic Zr 2 Cu phase forms first and then transforms to a tetragonal Zr 2 Cu phase, while the matrix transforms to an orthorhombic Zr3Fe phase. The strength of the Zr-Cu-Fe-Al composite containing cubic Zr 2 Cu phase and glass matrix increases, and the plasticity also improves compared to the as-cast Zr-Cu-Fe-Al bulk metallic glass. Our results suggest that the formation of multiple and complex crystalline products would be the characteristics of the Zr-Cu-Fe-Al glass with better glass-forming ability. Our study may shed light on the synthesis of bulk-sized glass-nanocrystals composites of high strength and good plasticity.

36 MATERIALS SCIENCE↗

Temperature–Programmed Separation of Hexane Isomers by a Porous Calcium Chloranilate Metal–Organic Framework

The full separation of alkane isomers as a function of different degrees of branching remains a daunting challenge due to its stringent requirement with respect to pore dimensions of the adsorbents. In this work, we report a novel microporous coordination network built on calcium (II) and chloranilate. The compound has a flexible framework and exhibits temperature-dependent adsorption behavior toward hexane isomers. At 30 °C, it accommodates substantial amounts of linear and monobranched hexanes but fully excludes their dibranched isomer, and at elevated temperatures such as 150 °C, it acts as a splitter for linear and branched alkanes. Its capability of efficient discrimination of hexane isomers as a function of branching is verified by experimental breakthrough measurements. Furthermore, ab initio calculations have uncovered the underlying selective size-exclusion separation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cobalt and nickel concentrations in the 'komatiite component' of Apollo 16 polymict samples

Some estimates for the concentrations of Co and Ni in the primitive mafic component of Apollo 16 breccias and soils are large, comparable to concentrations in terrestrial komatiites. These estimates may be erroneously high because the contribution from meteoritic contamination of the samples has been underestimated. However, even if the correction for meteoritic Co and Ni is valid and the calculated residual Ni is not of meteoritic origin, the Ni is presently carried by Fe-Ni metal while the Fe and Mg are carried by mafic silicates. If any large-scale separation of metal and silicate phases has occurred, the concentration ratio of Ni to Fe + Mg in the mafic silicates of the ancient crust in the vicinity of the Apollo 16 site has not been preserved by Apollo 16 rocks. Apollo 16 polymict breccias and soils contain much higher concentrations of siderophile elements and Fe-Ni metal than other nonmare samples from the Moon. Thus, it is likely that the Ni/(Mg + Fe) ratio estimated for the komatiite component from Apollo 16 samples is high compared to the actual ratio for the lunar crust.

Korotev, Randy L.↗

Capacitive connectors for digital-data lines

Proposed connector consisting of twin metal films separated by thin layers of insulating material transmits digital pulses capacitively. There is no direct contact between metal films; therefore, there is no ohmic contact drop and no wear when connections are changed. Since metal films are sealed in insulating material, there is no corrosion from exposure to atmosphere.

Studer, P. A.↗

A two-dimensional phase separation on the spherical surface of the metallic glass Au55Pb22.5Sb22.5

Recent experiments indicate that a phase separation in a spherical sample of the metallic glass Au55Pb22.5Sb22.5 occurs near the surface of the sphere. This strongly suggests either a contribution of surface-free energy to the decomposition process or a possible influence of near surface impurities absorbed during synthesis of the sphere. The surface phase separation has been studied as a function of cooling rate of the sphere. At high cooling rates (small sphere sizes), the surface separation disappears altogether suggesting that the surface of the parent liquid droplet is initially homogeneous.

Lee, M. C.↗

Two Cycling Centers in One Molecule: Communication by Through-Bond Interactions and Entanglement of the Unpaired Electrons

Many applications in quantum information science (QIS) rely on the ability to laser- cool molecules. The scope of applications can be expanded if laser-coolable molecules possess two or more cycling centers, i.e., moieties capable of scattering photons via multiple absorption-emission events. Here in this paper we employ equation-of-motion coupled-cluster method for double electron attachment (EOM-DEA-CCSD) to study the electronic structure of hypermetallic molecules with two alkaline earth metals connected by an acetylene linker. The electronic structure of the molecules is similar to that of two separated alkali metals; however, the interaction between the two electrons is weak and largely dominated by through-bond interactions. The communication between the two cycling centers is quantified by the extent of the entanglement of the two unpaired electrons associated with each center. This contribution highlights the rich electronic structure of hypermetallic molecules that may advance various applications in QIS and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing lanmodulin's mechanisms of rare-earth selectivity for protein-based bioseparations

Our BES Separation Science program project, DE-SC0021007, supported our efforts to begin to understand the mechanisms underlying selectivity of a novel class of lanthanide-binding proteins discovered by our laboratory, called lanmodulin (LanM), and to leverage these proteins for recovery and separations of trivalent rare earth elements (REEs) as well as of trivalent actinides. Overall, our work provides important insights into how higher-order (e.g., secondary, tertiary, and quaternary) protein structure modulates selectivity profiles of proteins that bind f-elements highly selectively. These results are important for advancing the concept of protein-based separations of REEs and, perhaps, of other critical minerals.

Lanmodulin, rare earth elements, protein-based met↗

Radiation-resistant metal-organic framework enables efficient separation of krypton fission gas from spent nuclear fuel

Capture and storage of volatile radionuclides that result from processing of used nuclear fuel is a major challenge. Solid adsorbents, in particular ultra-microporous metal-organic frameworks, could be effective in capturing these volatile radionuclides, including 85 Kr. However, metal-organic frameworks are found to have higher affinity for xenon than for krypton, and have comparable affinity for Kr and N 2 . Also, the adsorbent needs to have high radiation stability. To address these challenges, here we evaluate a series of ultra-microporous metal-organic frameworks, SIFSIX-3-M (M = Zn, Cu, Ni, Co, or Fe) for their capability in 85 Kr separation and storage using a two-bed breakthrough method. These materials were found to have higher Kr/N 2 selectivity than current benchmark materials, which leads to a notable decrease in the nuclear waste volume. The materials were systematically studied for gamma and beta irradiation stability, and SIFSIX-3-Cu is found to be the most radiation resistant.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

An Adsorptive Membrane Platform for Precision Ion Separation: Membrane Design and First‐Principles Studies

One of the key challenges in separation science is the lack of precise ion separation methods and mechanistic understanding crucial for efficiently recovering critical materials from complex aqueous matrices. Herein, first-principles electronic structure calculations and in situ Raman spectroscopy are studied to elucidate the factors governing ion discrimination in an adsorptive membrane specifically designed for transition metal ion separation. Density functional theory calculations and in situ Raman data jointly reveal the thermodynamically favorable binding preferences and detailed adsorption mechanisms for competing ions. How membrane binding preferences correlate with the electronic properties of ligands is explored, such as orbital hybridization and electron localization. The findings underscore the importance of the phenolate group in oxime ligands for achieving high selectivity among competing transition metal ions. In-depth understanding on which specific atomistic site within the microenvironment of metal-ligand binding pockets governs the ion discrimination behaviors of the host will build a solid foundation to guide the rational design of next-generation materials for precision separation essential for energy technologies and environment remediation. In tandem, synthetic controllability is demonstrated to transform 3D micrometer-scale crystals to a 2D crystalline selective layer in membranes, paving the way for more precise and sustainable advances in separation science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Topological effects on separation of alkane isomers in metal–organic frameworks

Polymorphism in metal–organic frameworks (MOFs) means that the same chemical building blocks (nodes and linkers) can be used to construct isomeric MOFs with different topological networks. The choice of topology can substantially impact the pore network of the MOF, changing the sizes and shapes of the pores, which has implications for adsorption and separation applications. Here, we look at the influence of topology in 38 polymorphic MOFs on the separation of linear and branched C4–C6 alkane isomers, a separation of great importance to the petrochemical industry. We find that the MOF Cu 2 (1,4-benzenedicarboxylate) in nbo topology (nbo-Cu 2 BDC) has particularly high affinity for linear alkanes due to its small pore size, which excludes the branched isomers. Upon studying this MOF in further detail, we find that it can take either of two conformations: a cubic conformation, which is typical of nbo MOFs, and a unique star conformation that contains 1D triangular and hexagonal channels. The determination of which conformation the MOF will adopt depends on steric effects between the nodes and linkers.

42 ENGINEERING↗

Removal and Deactivation of Bond Sodium from Fast Reactor Blanket Materials

The disposition of sodium-bonded spent nuclear fuel and blanket materials in a repository is complicated by the presence of sodium metal that is used as a thermal bond between the uranium metal fuel and blanket slugs and their cladding. The concern is that the metallic sodium could react with water, producing explosive hydrogen gas, or could exhibit a pyrophoric character. Thus, experimental studies were performed to investigate and demonstrate the removal and deactivation of bond sodium from blanket material in a dry environment. Specifically, bond sodium was removed from unirradiated Fermi-1 blanket elements and an assembly via a melt-drain-evaporate process using elevated temperature and reduced pressure. The effectiveness of sodium metal removal from the blanket materials and their associated cladding was =99.9998%, based on post-test quantitative analyses. The separated sodium metal was collected and subsequently deactivated by reacting it in a molten state with a controlled addition of ammonium chloride particles atop a molten salt medium. In this process sodium chloride is formed and assimilates into the salt pool. The subsequent deactivation of the bond sodium produced a solid ingot of sodium chloride, potassium chloride, lithium chloride, and cesium chloride that was devoid of sodium metal based on post-test analyses of the salt product. Both the sodium removal and deactivation operations were conducted within a dry inert atmosphere enclosure. The results of this study substantiate a path forward for the disposition of sodium-bonded blanket materials, including 34 metric tons heavy metal in irradiated Fermi-1 blanket material currently stored at Idaho National Laboratory.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Controlled Conversion of Sodium Metal From Nuclear Systems to Sodium Chloride

A series of three bench-scale experiments was performed to investigate the conversion of sodium metal to sodium chloride via reactions with non-metal and metal chlorides. Specifically, batches of molten sodium metal were separately contacted with ammonium chloride and ferrous chloride to form sodium chloride in both cases along with iron in the latter case. Additional ferrous chloride was added to two of the three batches to form low melting point consolidated mixtures of sodium chloride and ferrous chloride, whereas consolidation of a sodium-chloride product was performed in a separate batch. Samples of the products were characterized via X-ray diffraction to identify attendant compounds. The reaction of sodium metal with metered ammonium chloride particulate feeds proceeded without reaction excursions and produced pure colorless sodium chloride. The reaction of sodium metal with ferrous chloride yielded occasional reaction excursions as evidenced by temperature spikes and fuming ferrous chloride, producing a dark salt-metal mixture. This investigation into a method for controlled conversion of sodium metal to sodium chloride is particularly applicable to sodium containing elevated levels of radioactivity—including bond sodium from nuclear fuels—in remote-handled inert-atmosphere environments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Advanced Isotope Separation Technology for Fusion Fuel

Deuterium-tritium fusion is the easiest nuclear fusion reaction among known fusion reactions. Since tritium is extremely rare, it is artificially produced by irradiating lithium metal. The separation, isolation, and storage of the tritium isotope has been a major focus of the Savannah River Site (SRS) for many decades. Thermal diffusion, fractional absorption, and cryogenic distillation have all been used in the past, and each has significant operational and safety challenges. A process known as the Thermal Cycling Absorption Process (TCAP) was invented at SRS, and because of its overwhelming advantages in safety, efficiency, size, and reduced tritium inventory, it has replaced all other hydrogen isotope separation processes at SRS. Here, the working principles and current development of hydrogen isotope separation using TCAP at SRS are explained as a potential advanced isotope separation process for the fusion fuel cycle.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗