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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction

Chemical separations, particularly liquid extractions, are pervasive in academic and industrial laboratories, yet a mechanistic understanding of the events governing their function are obscured by interfacial phenomena that are notoriously difficult to measure. In this work, we investigate the fundamental steps of ligand self-assembly as driven by changes in the interfacial H-bonding network using vibrational sum frequency generation. Our results show how the bulk pH modulates the interfacial structure of extractants at the buried oil/aqueous interface via the formation of unique H-bonding networks that order and bridge ligands to produce self-assembled aggregates. These extended H-bonded structures are key to the subsequent extraction of Co2+ from the aqueous phase in promoting micelle formation and subsequent ejection of the said micelle into the oil phase. The combination of static and time-resolved measurements reveals the events underlying complexities of liquid extractions at high [Co2+]:[ligand] ratios by showing an evolution of interfacially assembled structures that are readily tuned on a chemical basis by altering the compositions of the aqueous phase. The results of this work point to new principles to design-applied separations through the manipulation of surface charge, electrostatic screening, and the associated H-bonding networks that arise at the interface to facilitate organization and subsequent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

One-Step Ligand-Exchange Method to Produce Quantum Dot–DNA Conjugates for DNA-Directed Self-Assembly

To address the current challenges in making bright, stable, and small DNA-functionalized quantum dots (QDs), we have developed a one-step ligand-exchange method to produce QD–DNA conjugates from commonly available hydrophobic QDs. We show that by systematically adjusting the reaction conditions such as ligand-to-nanoparticle molar ratio, pH, and solvent composition, stable and highly photoluminescent water-soluble QD–DNA conjugates with relatively high ligand loadings can be produced. Moreover, by site specifically binding these QD–DNA conjugates to a DNA origami template, we demonstrate that these bioconjugates have sufficient colloidal stability for DNA-directed self-assembly. Fluorescence quenching by an adjacent gold nanoparticle (AuNP) was demonstrated. Such QD–AuNP dimers may serve as biosensors with improved sensitivity and reproducibility. Furthermore, our simple method can facilitate the assembly of QDs into more complex superlattices and discrete clusters that may enable novel photophysical properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

One-Step Synthesis and Operando Electrochemical Impedance Spectroscopic Characterization of Heterostructured MoP–Mo 2 N Electrocatalysts for Stable Hydrogen Evolution Reaction

Here this study presents a novel synthesis of self-standing MoP and Mo 2 N heterostructured electrocatalysts with enhanced stability and catalytic performance. Facilitated by the controlled phase and interfacial microstructure, the seamless structures of these catalysts minimize internal resistivity and prevent local corrosion, contributing to increased stability. The chemical synthesis proceeds with etching step to activate the surface, followed by phosphor-nitriding in a chemical vapor deposition chamber to produce MoP-Mo 2 N@Mo heterostructured electrocatalysts. X-ray diffraction analyses confirm the presence of MoP, Mo 2 N, and Mo phases in the electrocatalyst. Morphology studies using scanning electron microscopy characterizes the hierarchical growth of structures, indicating successful formation of the heterostructure. X-ray photoelectron spectroscopy (XPS) analyses of the as-synthesized and post-catalytic activity samples reveal the chemical shift in terms of binding energy (BE) of Mo 3d XPS peak, especially after catalytic activity. The XPS BE shifts attributed to changes in oxidation state, electron transfer, and surface reconstruction during catalysis. Electrochemical evaluation of the catalysts demonstrates the superior performance of the MoP-Mo 2 N@Mo heterostructured catalyst in hydrogen evolution reactions (HER), with lower overpotentials and enhanced Tafel slopes. Stability tests reveal changes in double layer capacitance over time, suggesting surface reconstruction and increased active surface area during catalysis. Operando electrochemical impedance spectroscopy (EIS) further elucidates the dynamic changes in resistance and charge transfer during HER. Overall, comprehensive understanding of the synthesis, characterization, and electrochemical behavior of the developed MoP-Mo 2 N@Mo heterostructured electrocatalyst as presented in this paper highlights their potential utilization in sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Single-Step Nonthermal Plasma Synthesis of Water-Soluble and Near-Infrared-Emitting Si Quantum Dots for Bioimaging Applications

Here, we present a single-step nonthermal plasma method for the synthesis of near-infrared (NIR)-emitting and water-soluble Si quantum dots (QDs) for bioimaging applications. Oxygen gas and water vapor were introduced together with acrylic acid (AA) into the afterglow region of the synthesis plasma leading to the surface functionalization of the upstream synthesized Si QDs. The simultaneous surface oxidation and ligand grafting enabled solubility and colloidal stability of the Si QDs in water, as evidenced by strongly reduced hydrodynamic diameters. Aged Si QDs in water emitted NIR photoluminescence (PL) at around 830 nm. The PL quantum yield of the Si QDs in water increased over time from initially undetectable to ~30% after 8 days. Cell viability tests showed that >70% of 3T3 cells survived for 24 h at a concentration of 200 μg/mL of oxidized AA grafted Si QDs. The water solubility, NIR emission with a high quantum yield, and cell viability make the Si QDs promising for bioimaging applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Plasmon-Driven Ammonia Decomposition on Pd(111): Hole Transfer’s Role in Changing Rate-Limiting Steps

Here, ammonia (NH 3 ) has the potential to be a hydrogen carrier because it can be transported and stored with ease, but only if it also can be decomposed easily when needed. Understanding how to control the frequently rate-limiting N–H bond breaking and N–N bond forming on catalytic surfaces may help design efficient means for NH 3 decomposition. Yuan et al. recently demonstrated photocatalytically selective N–H bond breaking in NH 3 on plasmon-driven aluminum–palladium (Al–Pd) antenna–reactor heterostructures. Using embedded correlated wavefunction (ECW) theory, we predict that the rate-determining step (RDS) for NH 3 decomposition on Pd(111) via thermocatalysis (dissociating the first N–H bond, *NH 3 → *NH 2 + *H, in the ground state, where * means adsorbed) differs from that via photocatalysis (dissociating the second N–H bond, *NH 2 → *NH + *H, in the excited state). This result is consistent with the measured catalytic efficiency and selectivity of NH 3 -deuterium (D 2 ) exchange reactions (an indirect way to measure N–H bond breaking) on Al–Pd heterodimers. We also determine the origin of the observed selectivity of thermocatalysis and photocatalysis on Pd(111) toward doubly deuterated (NHD 2 ) and monodeuterated (NH 2 D) products, respectively, and explore viability of the full NH 3 decomposition path, also via ECW theory. Additionally, we predict that the associative desorption of *N as N 2 from Pd(111) is extremely difficult in thermocatalysis at least at low surface coverages; metal-to-adsorbate hole transfer in photocatalysis stabilizes the transition state for the first N–H bond dissociation, shifting the RDS to the second N–H bond breaking. Furthermore, the redistribution of electrons around *N upon excitation reduces the electron density in the Pd–N bonds, which may lower the barrier for N 2 associative desorption in photocatalysis. Thus, light-induced, plasmon-mediated, excited-state hole transfer may provide an efficient mechanism to accelerate NH 3 decomposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

One-Step Solution Patterning for Two-Dimensional Perovskite Nanoplate Arrays

Two-dimensional perovskite crystals have attracted significant attention for their diverse optoelectronic characteristics, owing to their superior semiconducting properties. However, the majority of studies to date have focused on single crystals, which pose challenges for integration into device arrays due to their incompatibility with selective growth or conventional lithography techniques. Here, a facile one-step solution process for synthesizing 2D perovskite crystal arrays is proposed through meniscus-guided coating on patterned substrates. Here we further utilized this method for the synthesis of lateral heterostructure nanoplate arrays. Six different 2D perovskite nanoplate arrays, including epitaxial heterostructures, are successfully realized. Optical and crystallographic characterizations show the high optical performance and crystallinity of the nanoplates. Moreover, this method is further employed to prepare high-performance 2D perovskite nanoplate photosensor arrays. This strategy can be utilized as a guideline for the fundamental investigation of optical properties and the development of high-performance optoelectronics of perovskite materials including photosensors and displays.

2D perovskite nanoplates↗
DOE OSTI2025

One-Step Transfer of Symmetric and Asymmetric Contacts for Large-Scale 2D Electronics and Optoelectronics

Two-dimensional (2D) semiconductors are highly promising candidates for thin-film transistor applications due to their scalability, transferability, atomic thickness, and relatively high carrier mobility. However, a substantial performance gap remains between individual devices based on single-crystalline 2D films and wafer-scale integrated circuits, primarily due to defects introduced during conventional fabrication processes. Here, we report a diamond-assisted electrode transfer technique for the van der Waals integration of wafer-scale prefabricated electrode arrays onto 2D materials, enabling scalable electronics and optoelectronics. Implemented on metal–organic chemical vapor deposition-grown monolayer molybdenum disulfide, this method forms ultraclean metal–semiconductor interfaces, yielding field-effect transistors with excellent ohmic contacts, a low contact resistance of 400 Ω·μm, and a Schottky barrier height of only 9 meV. Furthermore, we demonstrate a scalable transistor array on monolayer molybdenum disulfide with excellent device performance uniformity, achieving an average field-effect mobility of 30 cm 2 V –1 s –1 and an on/off current ratio exceeding 105. Additionally, high photocurrent and responsivity were demonstrated in the array devices, showing their potential for excellent image detection. We further demonstrate the versatility of this technique by fabricating a Schottky diode array through a single-step transfer of asymmetric electrodes─low work function aluminum and high work function gold─onto monolayer tungsten diselenide. This approach provides a clean, effective solution for contact engineering in 2D materials, offering a viable pathway toward wafer-scale, high-performance 2D electronics, optoelectronics, and integrated circuits.

2D electronics↗
DOE OSTI2020

Two-Step Patterning of Scalable All-Inorganic Halide Perovskite Arrays

Halide perovskites have many important optoelectronic properties, including high emission efficiency, high absorption coefficients, color purity, and tunable emission wavelength, which makes these materials promising for optoelectronic applications. However, the inability to precisely control large-scale patterned growth of halide perovskites limits their potential toward various device applications. Here, we report a patterning method for the growth of a cesium lead halide perovskite single crystal array. Our approach consists of two steps: (1) cesium halide salt arrays patterning and (2) chemical vapor transport process to convert salt arrays into single crystal perovskite arrays. Characterizations including energy-dispersive X-ray spectroscopy and photoluminescence have been employed to confirm the chemical compositions and the optical properties of the as-synthesized perovskite arrays. This patterning method enables the patterning of single crystal cesium lead halide perovskite arrays with tunable spacing (from 2 to 20 μm) and crystal size (from 200 nm to 1.2 μm) in high production yield (almost every pixel in the array is successfully grown with converted perovskite crystals). Furthermore, our large-scale patterning method renders a platform for the study of fundamental properties and opportunities for perovskite-based optoelectronic applications.

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

One Step Block-like Copolymers from an Upcycled Monomer Using Ring-Opening Metathesis Polymerization

Block-like copolymers can be readily synthesized in one step using monomers with widely separated reactivity ratios. Here, we show that trans,trans,trans-1,5,9-cyclododecatriene (CDT), produced from polybutadiene via cyclodepolymerization (CDP), undergoes gradient copolymerization via ring-opening metathesis polymerization (ROMP) with a selected norbornene monomer to produce a block-like copolymer that exhibits bulk nanophase separation and excellent thermomechanical performance. These data highlight a new ROMP copolymerization system with a sharp compositional drift and introduce a simple pathway to convert waste plastic into a valuable building block for high-value thermoplastic materials.

block copolymer↗
DOE OSTI2021

Technoeconomic Assessment of a Sequential Step-Leaching Process for Rare Earth Element Extraction from Acid Mine Drainage Precipitates

Herein, Coal waste products have been studied as a new source of Rare Earth Elements (REEs) and other Critical Minerals (CM) essential for the development of renewable energy technologies, but the economic viability of these source materials is not well understood. This paper examines the technoeconomic performance of a novel process for rare earth element extraction from acid mine drainage precipitates (AMDp) in the Appalachian Coal Basin. The three phase extraction process includes excavation and transportation of AMDp, multi-phase pH driven step-leaching of REEs at ambient conditions, and commercial solvent extraction to produce a saleable grade rare earth oxide material that can be reduced to a pure metal. We estimate the life-cycle cost of bench-scale extraction of REEs from two representative Appalachian AMDp feedstock chemistries at between 4000 – 6000 $/kg of mixed REE concentrate produced. Both the AMDp composition and process parameters affect the profitability of REE extraction, with the REE concentration and distribution of REE in the feedstock, extraction and precipitation reagent consumption rates, and the potential for reagent recycling as the key variables. Economically profitable valorization of REE from AMDp will require a combination of continued process innovation and sizable financial incentives to substantially influence domestic supply of REEs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Oxidative Catalytic Fractionation of Lignocellulosic Biomass Using a Co-N-P-C Catalyst and One-Step Isolation of Aromatic Monomers via Centrifugal Partition Chromatography

Methods for catalytic fractionation of biomass provide a means to convert lignin directly into monomers while generating a high-quality cellulosic stream, contrasting conventional biomass pretreatment strategies that prioritize the cellulosic fraction. Here, a nonprecious-metal Co-N-P-C catalyst is identified for aerobic oxidative catalytic fractionation (OCF) of poplar feedstock in dimethyl carbonate that achieves significantly higher yields of aromatic monomers (24 wt %) relative to those obtained with a recently reported Co-N-C catalyst in acetone solvent (15 wt %). Mechanistic studies indicate that the acidic properties of the catalyst contribute to its improved performance by promoting extraction of lignin from insoluble polysaccharides. This OCF process is complemented by the development of a new centrifugal partition chromatography (CPC) method that supports isolation of all five major aromatic monomers (syringic acid, syringaldehyde, vanillic acid, vanillin, and para-hydroxybenzoic acid) in a single liquid–liquid extraction purification step. Furthermore, this OCF/CPC sequence has important implications for future lignin valorization efforts.

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

Operando Contactless EFISH Study of the Rate-Determining Step of Light-Driven Water Oxidation on TiO 2 Photoanodes

For many slow solar-fuel-forming reactions, the accumulation of photogenerated minority carriers on the photoelectrode surface leads to light-induced band edge unpinning, affecting the junction properties by decreasing band bending in the semiconductor space charge layer and increasing the driving force of surface reactions in the electric double layer. In this study, we demonstrate a contactless operando electric field-induced second harmonic generation (EFISH) method for measuring the band bending change (δΔΦ SCR L ) on photoelectrodes upon photoexcitation. For ndoped rutile TiO 2 water oxidation photoanodes at pH 7, δΔΦ SCR L increases at more positive potentials or higher illumination power density until it reaches saturation values. We show that under fast mass transport conditions, δΔΦ SCR L is exclusively attributed to the accumulated charged rate-determining species that can be regarded as temporary surface states, and the relationship between the photocurrent and δΔΦ SCR L can be well modeled by assuming that hole trap states function as the reaction center. Kinetic isotope experiments identify proton-coupled electron transfer as the rate-determining step and suggest a possible chemical nature of the key intermediate. We demonstrate that light-induced band edge unpinning is a beneficial feature under high illumination conditions for oxygen evolution reaction on TiO 2 because it maintains the photon-to-current conversion efficiency by enhancing the surface reaction driving force, shedding light on the actual device application.

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

Iridium Nanocrystals Enriched with Defects and Atomic Steps to Enhance Oxygen Evolution Reaction Performance

The presence of defects can significantly improve catalytic activity and stability, as they influence the binding of the reactants, intermediates, and products to the catalyst. Controlling defects in the structures of nanocrystal catalysts is synthetically challenging. In this study, we demonstrate the ability to control the growth of Ir nanocrystals, enabling the tuning of both structural and surface defects. The Ir nanocrystals have unique structures that range from single crystals of a few nanometers to twinned nanoparticles and multiply twinned crystallites with a high density of atomic steps. Further, this approach of defect engineering enables us to understand their roles in enhancing the performance of the OER and producing an Ir catalyst with both high activity and stability. Our results show the importance of the concept of using synthetic control of structural and surface defects in metal nanoparticles as a strategy to improve catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Direct observation of dual-step twinning nucleation in hexagonal close-packed crystals

Design and processing of advanced lightweight structural alloys based on magnesium and titanium rely critically on a control over twinning which, however, remains elusive to date and is dependent on an explicit understanding on the twinning nucleation mechanism in hexagonal close-packed (HCP) crystals. Here, by using in-situ high resolution transmission electron microscopy, we directly reveal a “dual-step” twinning nucleation mechanism in HCP rhenium nanocrystals. It is found that nucleation of the predominant {10 -12} twinning is initiated by disconnections on the Prismatic¦Basal interfaces which establish the lattice correspondence of the twin with a minor deviation from the ideal orientation. Subsequently, the minor deviation is corrected by the formation of coherent twin boundaries through rearrangement of the disconnections on the Prismatic¦Basal interface; thereafter, the coherent twin boundaries propagate by twinning disconnections. The findings provide much-needed high-resolution evidences to the twinning nucleation mechanism in HCP crystals, with crucial implications for engineering advanced structural alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insight into multi-step geological evolution of C-type asteroids from Ryugu particles

C-type asteroids are the source of the carbonaceous chondrite meteorites and represent remnants of primitive planetesimals that formed at the outer margins of the early Solar System and may have delivered volatiles to the inner Solar System, in particular the early Earth. However, the nature of carbonaceous chondrites is not well understood owing to terrestrial alteration. Here, in this work, we present the petrology and mineral chemistry of surface materials collected by the Japan Aerospace Exploration Agency (JAXA) Hayabusa2 spacecraft from the C-type asteroid Ryugu. The Ryugu particles we studied are similar to CI (Ivuna-type) chondrites but with some important differences, such as the presence of Na–Mg phosphates and Na-rich phases and the lack of ferrihydrite and gypsum. Ryugu particles experienced several steps of aqueous alteration, metasomatism and brecciation under variable conditions. These materials represent mixed lithologies and formed at different locations within their parent asteroid. The evidence presented here demonstrates that the C-type asteroid Ryugu experienced a complex geologic evolution shortly after its formation.

58 GEOSCIENCES↗
DOE OSTI2021

Structural and mechanistic insights into the bifunctional HISN2 enzyme catalyzing the second and third steps of histidine biosynthesis in plants

The second and third steps of the histidine biosynthetic pathway (HBP) in plants are catalyzed by a bifunctional enzyme–HISN2. The enzyme consists of two distinct domains, active respectively as a phosphoribosyl-AMP cyclohydrolase (PRA-CH) and phosphoribosyl-ATP pyrophosphatase (PRA-PH). The domains are analogous to single-domain enzymes encoded by bacterial hisI and hisE genes, respectively. The calculated sequence similarity networks between HISN2 analogs from prokaryotes and eukaryotes suggest that the plant enzymes are closest relatives of those in the class of Deltaproteobacteria. In this work, we obtained crystal structures of HISN2 enzyme from Medicago truncatula (MtHISN2) and described its architecture and interactions with AMP. The AMP molecule bound to the PRA-PH domain shows positioning of the N1-phosphoribosyl relevant to catalysis. AMP bound to the PRA-CH domain mimics a part of the substrate, giving insights into the reaction mechanism. The latter interaction also arises as a possible second-tier regulatory mechanism of the HBP flux, as indicated by inhibition assays and isothermal titration calorimetry.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Bioinformatics of cyanophycin metabolism genes and characterization of promiscuous isoaspartyl dipeptidases that catalyze the final step of cyanophycin degradation

Cyanophycin is a bacterial biopolymer used for storage of fixed nitrogen. It is composed of a backbone of L-aspartate residues with L-arginines attached to each of their side chains. Cyanophycin is produced by cyanophycin synthetase 1 (CphA1) using Arg, Asp and ATP, and is degraded in two steps. First, cyanophycinase breaks down the backbone peptide bonds, releasing β-Asp-Arg dipeptides. Then, these dipeptides are broken down into free Asp and Arg by enzymes with isoaspartyl dipeptidase activity. Two bacterial enzymes are known to possess promiscuous isoaspartyl dipeptidase activity: isoaspartyl dipeptidase (IadA) and isoaspartyl aminopeptidase (IaaA). We performed a bioinformatic analysis to investigate whether genes for cyanophycin metabolism enzymes cluster together or are spread around the microbial genomes. Many genomes showed incomplete contingents of known cyanophycin metabolizing genes, with different patterns in various bacterial clades. Cyanophycin synthetase and cyanophycinase are usually clustered together when recognizable genes for each are found within a genome. Cyanophycinase and isoaspartyl dipeptidase genes typically cluster within genomes lacking cphA1. About one-third of genomes with genes for CphA1, cyanophycinase and IaaA show these genes clustered together, while the proportion is around one-sixth for CphA1, cyanophycinase and IadA. We used X-ray crystallography and biochemical studies to characterize an IadA and an IaaA from two such clusters, in Leucothrix mucor and Roseivivax halodurans, respectively. The enzymes retained their promiscuous nature, showing that being associated with cyanophycin-related genes did not make them specific for β-Asp-Arg dipeptides derived from cyanophycin degradation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

One-step lignocellulose depolymerization and saccharification to high sugar yield and less condensed isolated lignin

The cost of sugar production remains a key challenge in future lignocellulosic biorefineries. We demonstrate that ZnBr 2 , an inexpensive inorganic salt, provides nearly theoretical yields of glucose and xylose in one-step from poplar wood at 85 °C and short reaction times at molten salt hydrate (MSH) conditions without an acid. Catalytic depolymerization of the isolated MSH lignin, using a CoS 2 catalyst, yields 17% phenol-like monomers compared to only 1% produced from the acidified MSH lignin. Reductive catalytic fractionation of MSH lignin over Ru/C resulted in two times higher total monomer yield compared to the AMSH lignin. Both the lignin samples were characterized using 2D HSQC NMR and the thioacidolysis method. Thioacidolysis studies reveal 8.4% and 1.8% of β-O-4 linkages in MSH and acidified MSH lignin, respectively. Thermodynamic modeling and 13 C NMR spectroscopy indicate that the effectiveness of this catalyst arises from the strong interaction of the Lewis acidic zinc cation (Zn 2+ ) with the coordinated water molecules resulting in hydrolysis of the metal aquo complex and to the salt-driven increase in the H + activity coefficient. Techno-economic analysis demonstrates that despite being slower, the ZnBr 2 MSH media has cost advantages, compared to conventional hydrolysis and even to the LiBr and ZnBr 2 AMSH, due to the higher quality of lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗