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Shin, Sun Hae Ra

Publications and source records attributed to Shin, Sun Hae Ra.

Chelation-Driven Chemistry Controls Dissolution Pathways for Facile Critical Mineral Recovery from Ultramafic Resources

The efficient recovery of critical minerals, such as nickel (Ni) and manganese (Mn) from the subsurface is of vital importance, given their role in modern technologies ranging from batteries to advanced alloys. This study explores an approach that employs chelation to enhance critical mineral recovery from ultramafic rocks using chelating ligands under ambient pressures and systematically evaluates the extraction process for the first time. Experimental results demonstrate the superior performance of EDTA and PrDTA in achieving high extraction efficiencies for both Ni and Mn. To further highlight the ability for optimization, the fluid exchange and variation of fluid-to-rock ratio experiments were conducted, revealing tunable controls for engineering recovery. We show that under optimized conditions, a Ni extraction efficiency of ?82% and a Mn extraction efficiency of ~60% is achieved at ambient pressures, which is equivalent to over 23 times the current global Ni production, and 2 million metric tonnes (MMT) greater than the current global Mn production. From both in-situ and ex-situ mining perspectives, the results highlight the potential of chelation to advance sustainable mineral processing. Overall, this work highlights the environmental benefits of innovative ligand-assisted recovery methods, addressing the critical need for the efficient utilization of olivine resources.

Krishnan, Keerthana↗

Magnetic Nanoparticle Extraction of Lithium from Produced Waters - CRADA 483 (Final Report)

The demand for lithium in the energy production industry is expected to increase sharply, development of simple and cost-effective techniques for lithium production and recovery from various lithium sources is essential. In this project, core/shell magnetic nanoparticles were successfully designed to selectively extract lithium from aqueous lithium sources as an extension of Pacific Northwest National Laboratory’s magnetic nanofluid extraction technology. The core/shell magnetic nanoparticles are composed of manganese oxide-based lithium ion sieve shells, which allow selective lithium uptake from brines with multiple coexisting ions, over iron oxide cores, which can respond to external magnetic fields for effective recovery and reuse of adsorbents from a liquid. The synthesized lithium ion-sieves and core/shell magnetic nanoparticles were characterized using several techniques to reveal their crystallinity and morphology. The lithium uptake properties of the lithium ion-sieves and core/shell magnetic nanoparticles were evaluated in terms of lithium adsorption capacity, removal percentage, selectivity, and cycling performance in simulated and natural brines. Magnetic properties of the core/shell magnetic nanoparticles were tested by measuring magnetic saturation, and magnetic response of colloidal solutions containing the core/shell magnetic nanoparticles was tested with permanent magnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen sensing in different hydrogen-carrying gases using composites of PdSnO 2 and halloysite nanotubes

Here, in this work, we developed composites of palladium-decorated tin dioxide (PdSnO 2 ) and halloysite nanotubes (HNTs) by adding different amounts of HNTs as additives into PdSnO 2 , and investigated how the different amounts of HNTs in the composites and the different hydrogen (H 2 ) carrying gases (air and helium (He)) could affect the H 2 sensing performance of such composites (PdSnO 2 -HNT). Through the sensing-performance characterization using H 2 carried by air, it was found that PdSnO 2 with an appropriate small amount of HNTs (i.e., 2 % of PdSnO 2 mass) can improve the sensing performance with respect to limit of detection (LOD) and response/recovery time. Further, the optimal PdSnO2-HNT composite as a sensor was tested to detect H 2 in He. The testing results indicated that the composite can detect H 2 in He, but its performance parameters (i.e., the profile of calibration curve, LOD, and response time) are different from those of such a sensor in detecting H 2 in air. Moreover, the composite still presented better sensing performance than PdSnO 2 without HNTs in detecting H 2 in He. Possible reasons for the effects of HNT and H 2 -carrying gas on the sensing performance of PdSnO 2 -HNT-based sensors were discussed. We believe that this study provides valuable insights into the functionality and the adaptability of PdSnO 2 -HNT-based H 2 sensors in diverse operational conditions.

36 MATERIALS SCIENCE↗

Nuclear Energy Critical Material Waste Minimization Enabled by AM Techniques

This project provides evidence of the successful recycling of solid waste offcuts resulting from conventional manufacturing processes from three relevant alloys to next-generation nuclear reactor developers, providing a potentially upscalable circular process where no critical elements will be lost. Furthermore, iMOF-based adsorbents were successfully designed for CM extraction from aqueous solution, thereby providing a pathway for future upscaling for salvaging dissolved Ni ions. This research has achieved its goal of showing the impact of novel applications of recycling technologies for solid and liquid wastes that can be upscaled for application.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Role of Solvent in the Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces

Abstract A controlled growth of two‐dimensional (2D) π‐conjugated metal‐organic frameworks (MOFs) on solid substrates can open exciting opportunities for the application of 2D MOFs as optoelectronic devices. Some factors like solvent composition and type of substrates are known to influence the properties of solution‐processed 2D MOF crystals; however, a mechanistic understanding of how interactions between solvent, substrate, and precursors affect heterogeneous nucleation has been limited. Here, it is reported that the structure of Ni‐catecholate (Ni‐CAT‐1) MOFs at a solid–liquid interface is controlled by solvent–substrate and solvent–MOF precursor interactions. Specifically, the structure of the MOF film can be controlled by varying the affinity of the solvent to the substrate. As a fraction of N , N ‐dimethylformamide (DMF) in a binary solvent mixture of water and DMF increases, the arrangement of Ni‐CAT‐1 crystals varies from vertically aligned nanorods to the graphite substrate to less ordered nanorods with the lower initial nucleation number density of Ni‐CAT‐1 crystals on the surface.

2D materials↗

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↗

Self‐Assembly and Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces

Abstract Two‐dimensional (2D) conductive metal‐organic frameworks (MOF) represent a unique class of electrode materials with high capacity and power density. Understanding molecular mechanisms and pathways for heterogeneous nucleation of 2D π‐conjugated MOFs is highly desirable for controlling the structure and properties of conductive MOFs on solid substrates. Herein, a systematic study of nucleation and growth of 2D π‐conjugated Ni‐catecholate (Ni‐CAT‐1) MOFs on highly oriented pyrolytic graphite (HOPG) and copper substrates is reported. It is discovered that the nucleation density and growth kinetics of the MOF film can be controlled by varying substrate interactions with the organic linker. Specifically, π–π interactions between the linker and the HOPG dictate lower nucleation density, whereas π–metal interactions between the linker and the copper substrate dictate faster nucleation and higher nucleation densities. These studies reveal the key mechanism for Ni‐CAT‐1 nucleation on different surfaces and provide insights into interfacial control over the growth of other 2D π‐conjugated MOF films on solid substrates to inform synthesis of functional materials.

2D materials↗

Hierarchical assembly of ZnO nanowire trunks decorated with ZnO nanosheets for lithium ion battery anodes

Hierarchical architectures composed of nanomaterials in different forms are essential to improve the performance of lithium-ion battery (LIB) anodes. Here, we systematically studied the effects of hierarchical ZnO nanostructures on the electrochemical performance of LIBs. ZnO nanowire (NW) trunks were decorated with ZnO NWs or ZnO nanosheets (NSs) by successive hydrothermal synthesis to create hierarchical three-dimensional nanostructures. The branched ZnO NSs on the ZnO NW trunk exhibited a two-fold higher specific gravimetric capacity compared to ZnO NWs and branched ZnO NWs on ZnO NW trunks after 100 cycles of charging–discharging at 0.2C (197.4 mA g –1 ). The improvement in battery anode performance is attributable to the increased interfacial area between the electrodes and electrolyte, and the void space of the branched NSs that facilitates lithium ion transport and volume changes during cycling.

25 ENERGY STORAGE↗