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Hwang, Sooyeon

Publications and source records attributed to Hwang, Sooyeon.

14 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Circumventing thermodynamic limitations in converting carbon dioxide into carbon nanotubes via tandem catalysis

Carbon nanotubes (CNTs) are important materials for electronics and structural composites, but their production still relies on hydrocarbon-based chemical vapor deposition, an energy-intensive and fossil-dependent process, limited by rapid catalyst deactivation. Using CO2 as a carbon feedstock offers a sustainable route for CNT synthesis, yet direct CO2 conversion to CNTs is thermodynamically unfavorable and existing CO2-to-carbon pathways mainly yield amorphous or weakly graphitized solids. Here, we demonstrate a tandem electrochemical–thermochemical (EC-TC) strategy that overcomes these limitations. CO2 is first electrochemically reduced to a tunable mixture of C2H4 and CO, which is directly fed into a thermochemical reactor and converted into CNTs with controllable morphology and high CNT-to-metal mass ratios (~200) over NiFe catalysts at 750 °C. In situ synchrotron-based characterization and density functional theory calculations reveal that CO dissociation and C2H4 decomposition on NiFe alloys cooperatively promote CNT nucleation and sustained growth. This EC-TC strategy establishes a modular route for converting CO2 into value-added carbon nanomaterials.

03 NATURAL GAS↗
DOE OSTI2024

Surface Self-Diffusion Induced Sintering of Nanoparticles

Despite the critical role of sintering phenomena in constraining the long-term durability of nanosized particles, a clear understanding of nanoparticle sintering has remained elusive due to the challenges in atomically tracking the neck initiation and discerning different mechanisms. Through the integration of in situ transmission electron microscopy and atomistic modeling, this study uncovers the atomic dynamics governing the neck initiation of Pt–Fe nanoparticles via a surface self-diffusion process, allowing for coalescence without significant particle movement. Real-time imaging reveals that thermally activated surface morphology changes in individual nanoparticles induce significant surface self-diffusion. Further, the kinetic entrapment of self-diffusing atoms in the gaps between closely spaced nanoparticles leads to the nucleation and growth of atomic layers for neck formation. This surface self-diffusion-driven sintering process is activated at a relatively lower temperature compared to the classic Ostwald ripening and particle migration and coalescence processes. The fundamental insights have practical implications for manipulating the morphology, size distribution, and stability of nanostructures by leveraging surface self-diffusion processes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Laser-engraved defects in TiO 2 support: Enhancing reducibility and redox capability of Pt/TiO 2 catalyst for reactive and selective hydrogenation

Titanium dioxide (TiO 2 ) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here, in this work, we applied laser engraving to the anatase TiO 2 and studied the consequent changes in its structure and property as well as the properties of TiO 2 supported platinum (i.e., Pt/TiO 2 ) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (O v ) and Ti 3+ ) in anatase TiO 2 . This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO 2 . The defective TiO 2 is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO 2 catalyst is stronger than that of the pristine Pt/TiO 2 catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO 2 has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.

25 ENERGY STORAGE↗
DOE OSTI2024

Breaking Barriers in Chalcogenide Perovskite Synthesis: A Generalized Framework for Fabrication of BaMS 3 (M═Ti, Zr, Hf) Materials

Abstract Chalcogenide perovskites have garnered increasing attention as stable, non‐toxic alternatives to lead halide perovskites. However, their conventional synthesis at high temperatures (>1000 °C) has hindered widespread adoption. Recent studies have developed low‐to‐moderate temperature synthesis methods (<600 °C) using reactive precursors, yet a comprehensive understanding of the pivotal factors affecting reproducibility and repeatability remains elusive. This study delineates the critical factors in the low‐temperature synthesis of BaMS 3 (M═Zr, Hf, Ti) compounds and presents a generalized framework. Innovative approaches are developed for synthesizing BaMS 3 compounds using this framework involving organometallics for solution deposition. The molecular precursor routes, employing metal acetylacetonates to generate soluble metal–sulfur bonded complexes and metal–organic compounds to produce soluble metal‐thiolate, metal‐isothiocyanate, and metal‐trithiocarbonate species, are demonstrated to yield carbon‐free BaMS 3 . These methods have achieved the most contiguous films of BaZrS 3 and BaHfS 3 using solution deposition to date. Furthermore, a hybrid solution processing method involving stacking sputter‐deposited Zr and solution‐deposited BaS layers is employed to synthesize a contiguous, oxygen‐free BaZrS 3 film. The diffuse reflectance measurements indicate a direct bandgap of ≈ 1.85 eV for the BaZrS 3 films and ≈ 2.1 eV for the BaHfS 3 film under investigation.

25 ENERGY STORAGE↗
DOE OSTI2024

Defect-engineered monolayer MoS 2 with enhanced memristive and synaptic functionality for neuromorphic computing

Two-dimensional transition metal dichalcogenides (TMDs)-based memristors are promising candidates for realizing artificial synapses in next-generation computing. However, practical implementation faces several challenges, such as high non-linearity and asymmetry in synaptic weight updates, limited dynamic range, and cycle-to-cycle variability. Here, utilizing optimal-power argon plasma treatment, we significantly enhance the performance matrix of memristors fabricated from monolayer MoS 2 . Our approach not only improves linearity and symmetry in synaptic weight updates but also increases the number of available synaptic weight updates and enhances Spike-Time Dependent Plasticity. Notably, it broadens the switching ratio by two orders, minimizes cycle-to-cycle variability, reduces non-linear factors, and achieves an energy consumption of ~30 fJ per synaptic event. Implementation of these enhancements is demonstrated through Artificial Neural Network simulations, yielding a learning accuracy of ~97% on the MNIST hand-written digits dataset. Our findings underscore the significance of defect engineering as a powerful tool in advancing the synaptic functionality of memristors.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Surface Electronic Structure of Cr Doped Bi 2 Se 3 Single Crystals

Here, by using angle-resolved photoemission spectroscopy, we showed that Bi 2-x Cr x Se 3 single crystals have a distinctly well-defined band structure with a large bulk band gap and undistorted topological surface states. These spectral features are unlike their thin film forms in which a large nonmagnetic gap with a distorted band structure was reported. We further provide laser-based high resolution photoemission data which reveal a Dirac point gap even in the pristine sample. The gap becomes more pronounced with Cr doping into the bulk of Bi 2 Se 3 . These observations show that the Dirac point can be modified by the magnetic impurities as well as the light source.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evolution of the Fermi Surface of 1T-VSe 2 across a Structural Phase Transition

Periodic lattice distortion, known as the charge density wave, is generally attributed to electron–phonon coupling. This correlation is expected to induce a pseudogap at the Fermi level in order to gain the required energy for stable lattice distortion. The transition metal dichalcogenide 1T-VSe 2 also undergoes such a transition at 110 K. Here, we present detailed angle-resolved photoemission spectroscopy experiments to investigate the electronic structure in 1T-VSe 2 across the structural transition. Previously reported warping of the electronic structure and the energy shift of a secondary peak near the Fermi level as the origin of the charge density wave phase are shown to be temperature independent and hence cannot be attributed to the structural transition. Our work reveals new states that were not resolved in previous studies. Earlier results can be explained by the different dispersion natures of these states and temperature-induced broadening. Only the overall size of the Fermi surface is found to change across the structural transition. These observations, quite different from the charge density wave scenario commonly considered for 1T-VSe 2 and other transition metal dichalcogenides, bring fresh perspectives toward correctly describing structural transitions. Therefore, these new results can be applied to material families in which the origin of the structural transition has not been resolved.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Designing Li-ion battery cathodes free from critical raw materials such as Co and Ni has a huge technological and societal impact. Though anion redox-based Li-rich oxide cathodes allow designing Co and Ni free cathode compositions, the Li-rich oxides witnessed voltage fade, voltage hysteresis, and irreversible oxygen release despite their high capacity. Conversely, anion redox through highly covalent chalcogenides (S/Se) is emerging due to the improved covalency between metal d and ligand p bands. Here, we investigate the tuning of multi-chalcogen (S/Se) p-band and redox-active metal d-band in a model Li-rich chalcogen composition Li 1.13 Ti 0.57 Fe 0.3 S 2-y Se y (y = 0 - 1) through in-depth electrochemical, X-ray spectroscopy, and DFT-based electronic structure investigations. Introducing the appropriate amount of Se p band character in anion redox sulfides increases interlayer distance and metal - ligand covalency without modifying the original crystal structure, promoting significant electrochemical reversibility through mixed anionic (Se 2- /Se n- , S 2- /S n- , wherein n<2) and cationic (Fe 2+ /Fe 3+ ) redox reactions. Here we show the detailed Fe, S, and Se redox contributions during Li insertion/extraction through X-ray Absorption (XAS) and Hard X-ray Photoemission Spectroscopy (HAXPES) measurements. The orbital tuning approach improves rate capability for more than 10 C charge-discharge rate, exhibiting more than 50% of its original capacity obtained at C/20 rate. The buffer cation in the lattice (Ti 4+ ) remains electrochemically inactive even after significant Se p-band introduction in the sulfide framework. Overall, this work takes advantage of multi-anion redox chemistry to uncover practically demanding fast charging-discharging characteristics in intercalation cathodes. The obtained knowledge of this design can be extended to other oxide and chalcogen cathodes for high performance Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Confining platinum clusters in indium-modified ZSM-5 zeolite to promote propane dehydrogenation

Designing highly active and stable catalytic sites is often challenging due to the complex synthesis procedure and the agglomeration of active sites during high-temperature reactions. Here, we report a facile two-step method to synthesize Pt clusters confined by In-modified ZSM-5 zeolite. In-situ characterization confirms that In is located at the extra-framework position of ZSM-5 as In + , and the Pt clusters are stabilized by the In-ZSM-5 zeolite. The resulting Pt clusters confined in In-ZSM-5 show excellent propane conversion, propylene selectivity, and catalytic stability, outperforming monometallic Pt, In, and bimetallic PtIn alloys. The incorporation of In + in ZSM-5 neutralizes Brønsted acid sites to inhibit side reactions, as well as tunes the electronic properties of Pt clusters to facilitate propane activation and propylene desorption. The strategy of combining precious metal clusters with metal cation-exchanged zeolites opens the avenue to develop stable heterogeneous catalysts for other reaction systems.

58 GEOSCIENCES↗
DOE OSTI2024

Near Room Temperature Solvothermal Growth of Ferroelectric CsPbBr 3 Nanoplatelets with Ultralow Dark Current

CsPbBr 3 exhibits outstanding optoelectronic properties and thermal stability, making it a coveted material for detectors, light-emitting diodes, and solar cells. Despite observations of ferroelectricity in CsPbBr 3 quantum dots, synthesizing bulk ferroelectric CsPbBr 3 crystals has remained elusive, hindering its potential in next-generation optoelectronic devices like optical switches and ferroelectric photovoltaics. Here, a breakthrough is reported: a novel solvothermal technique enabling the growth of ferroelectric CsPbBr 3 nanoplatelets with lateral dimensions in the tens of micrometers. This represents a significant step toward achieving large-area ferroelectric CsPbBr 3 crystals. Unlike traditional methods, this approach allows for growth and crystallization of CsPbBr 3 in alcohol solutions by enhancing precursor solubility. Further this study confirms the ferroelectric nature of these nanoplatelets using second harmonic generation, electrical characterizations, and piezoresponse force microscopy. This work paves the way for utilizing ferroelectric CsPbBr 3 in novel optoelectronic devices, significantly expanding the potential of this material and opening doors for further exploration in this exciting field.

25 ENERGY STORAGE↗
DOE OSTI2024

In Situ TEM for Structural and Chemical Evolutions of Bimetallic Pt–Ni Nanoparticles at Elevated Temperatures: Implications for Heterogeneous Catalysis

Platinum-based bimetallic nanoparticles (NPs) are of great interest for their applications in catalysis. The catalytic properties of these NPs are significantly dependent on their morphology, structure, and composition, whose response to thermal input remains challenging to be fully understood. This study investigates the thermally induced structural and chemical evolutions of single-crystalline Pt-Ni NPs using in situ transmission electron microscopy. The observed morphological evolution includes the facet development from a truncated octahedron to a spherical-like isotropic shape, followed by the formation of pancake-like ellipsoid shape at high temperatures due to surface atom migration and interfacial wetting enabled by the particle-substrate interaction. Comparative investigations by in situ scanning transmission electron microscopy with energy dispersive X-ray spectroscopy mapping elucidate that the solid-solution compositional configuration can be retained over a large temperature range, while core-shell NPs undergo irreversible solid-solution transitions through chemical homogenization at elevated temperatures. Finally, these findings elucidate the effect of thermal input on structural evolution and compositional redistribution of Pt-Ni bimetallic NPs, offering valuable insights into the design of heterogeneous catalysts.

25 ENERGY STORAGE↗
DOE OSTI2024

CO 2 hydrogenation over rhodium cluster catalyst nucleated within a manganese oxide framework

Rhodium-based manganese oxide frameworks were explored as a prototype for carbon dioxide reactive capture and conversion. Three-dimensional frameworks of MnOx were utilized as support structures to isolate Rh metal centers. V, Na, and Zn were introduced as counterions to stabilize the structure and for their beneficial effect as promoters. Here, with this multicomponent catalyst, Rh active centers with MnOxs and varied counterions, we were able to selectively tune the catalytic performance of the material via the choice of counterion and structure of the host material. With cryptomelane-type tunnel manganese oxides octahedral molecular sieve (OMS2), we found that Rh-V-OMS2 was highly stable even after 48 hours on stream with a reaction rate of around 1.5x10 -4 mol CO 2 /g Rh /s, surpassing the net reactivity of other initially more active combinations. Furthermore, during CO 2 hydrogenation, in situ XAFS showed that single Rh atoms nucleated into nanoparticles/ sub-nanometer clusters with a coordination number of 5.5 or less. Our finding of the correlation between the reaction rate and particle size offers the potential for enhanced control over the reaction rate by tuning particle size. Our activity study with control experiments demonstrates that the activities of the catalysts are proved due to the unique metal support interaction offered by the Rh-X-MnO.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

Traditional Li-ion intercalation chemistry into graphite anode exclusively utilizes the co-intercalation-free or co-intercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfied cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in-situ synthesis of t-THF-GICs in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GICs and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional co-intercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10,000 cycles. Full cells coupled with layered cathode, display remarkable cycling stability upon a 15-min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach to achieving fast-charging and low-temperature batteries.

25 ENERGY STORAGE↗