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Results for “Analytical Chemistry”

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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Anisotropic Hot Spot Formation at a Grain Boundary in Shock-Compressed TATB High Explosive Crystal

Secondary high explosives (HEs) exhibit rich microstructure that promotes the formation of hot spots responsible for detonation initiation, but the role of microstructural interfaces remains poorly quantified. To this end, we develop extensions for the generalized crystal-cutting method (GCCM) to prepare molecular dynamics (MD) simulation cells containing grain boundaries (GBs) and other crystal–crystal interfaces with prescribed tilt and twist orientations. Using the GCCM, we perform MD simulations of shock interactions with a GB between the (001) and (100) crystal facets in the secondary HE TATB (1,3,5-triamino-2,4,6-trinitrobenzene). Our MD simulations reveal a strong directional dependence to the formation of a hot spot at the GB interface. In particular, transmission of the shock from the (001) grain to the (100) grain yields a hot spot in the (100) grain at the GB interface, whereas no hot spot is produced when an equivalent shock transits the GB in the opposite direction. We trace the origin of this GB anisotropy to three dominant factors: (1) the intrinsic differences in shock-deformation mechanisms and wave structures for the bulk (100) and (001) grains, which leads to distinct geometries and mechanical impedances upon shock arrival to the GB depending on which grains are donor or acceptor for the transmitted shock; (2) the different time intervals separating the initial shock rise and the formation of steady wave structures in the respective donor–acceptor configurations; and (3) the differences in time scales required to re-establish local thermal equilibrium. Interfacial hot spots form when these factors combine to impede development of a steady two-wave structure and instead induce a localized, pseudosingly shocked region that undergoes a higher rate of work production (resulting in a higher temperature) compared to when the steady two-wave structure develops further from the interface. The extensions to the GCCM approach presented here are anticipated to facilitate a wide range of MD studies that focus on understanding the role of crystal–crystal interfaces in molecular materials.

organic↗
DOE OSTI2025

Basin-Size Mapping: Prediction of Metastable Polymorph Synthesizability Across TaC–TaN Alloys

The sizes of the basins of attraction on the potential energy surface are helpful indicators in determining the experimental synthesizability of metastable phases. In principle, these basins can be controlled with changes in thermodynamic conditions such as composition, pressure, and surface energy. Herein, we use random structure sampling to computationally study how alloying smoothly perturbs basin of attraction sizes. The TaC 1-x N x pseudobinary is an ideal test system given the structural and polymorphic contrast of its parent compounds and their technological relevance as epitaxial substrates for Al 1-x Ga x N. While we find limited thermodynamic stability across all computationally observed phases, random structure sampling shows a significant composition region where the rocksalt basin dominates. As such, we predict the potential for the nonequilibrium synthesis of metastable rocksalt TaC 1-x N x alloys as substrates for Al 1-x Ga x N. At higher nitrogen concentrations, other low-energy metastable polymorphs emerge that continue to retain the hexagonal close packing suitable for III-N growth. Confidence in these trends was established through uncertainty quantification of the basin sizes and energy distributions; such analysis utilized the Beta and Dirichlet distributions. In conclusion, we also find (a) polymorph basin sizes can be rationalized in terms of energetic preferences for different coordination environments; and (b) basin sizes universally shrink with increasing nitrogen content, making the system more prone to amorphous growth.

36 MATERIALS SCIENCE↗
DOE OSTI2026

2D nanoconfinement distorts the solvation structure of hydroxide but not of hydronium

Understanding ion-specific behavior in nanoconfined water is essential for controlling charge transport and selectivity in two-dimensional membranes. Motivated by recent experiments revealing anomalous dielectric and transport behavior of water confined between hBN sheets, we use machine-learning-accelerated first-principles molecular dynamics to investigate the interfacial propensities of hydronium and hydroxide ions under similar confinement. We find that hydronium remains interfacial across all confinement regimes, whereas hydroxide shifts toward the interior as the environment becomes more bulk-like. This contrasting behavior reflects the combined influence of hydrogen bonding, interfacial water layering, and the polarization of hBN, which collectively stabilize hydronium at the surface while making hydroxide slightly more favorable within the structured interior. These findings expose an asymmetry in ion-surface coupling and establish a microscopic origin for hydronium’s enhanced interfacial affinity. The results provide mechanistic insight into ion partitioning in two-dimensional channels and highlight the collective structuring of confined water as a key determinant of interfacial ion thermodynamics.

organic↗
DOE OSTI2025

Techno-Economic Analysis and Life Cycle Assessment for the Separation of 2,3-Butanediol from Fermentation Broth Using Liquid–Liquid Extraction

It is energy-intensive to separate dilute 2,3-butanediol (2,3-BDO) (<10 wt %) from the aqueous phase of fermentation broth for sustainable aviation fuel (SAF) using conventional distillation. Liquid–liquid extraction (LLE) using oleyl alcohol as a solvent in a membrane extractor to extract BDO from water can significantly reduce the energy cost and minimize the potential emulsion. In an Aspen Plus model simulation, 95.2% BDO recovery and 97.1% BDO purity have been achieved using this LLE method with solvent recovery and heat integration. Here, the thermal energy cost was estimated to be 4.57 MJ/kg BDO, which is only about 16.8% of the lower heating value (LHV) of the BDO. This method consumes 81% less energy than the cascade distillation and reduces about $0.46/GGE (gasoline gallon equivalent) to the minimal fuel selling price. Meanwhile, the greenhouse gas (GHG) emission is 62% lower than petroleum-based jet fuel production and 34% less than using the cascade distillation.

09 BIOMASS FUELS↗
DOE OSTI2025

Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds

Currently, there are few examples of circularly recyclable polymers with all-carbon backbones, probably owing to the challenge of using selective C–C bond cleavage to efficiently produce monomers in recycling processes. Furthermore, here we demonstrate a series of biologically sourced polymuconate polymers synthesized via simple free-radical polymerization that exhibit intrinsically weakened C–C bonds and controlled chemical recycling to monomers. Modifying the side chains and copolymerization ratios allows a wide range of mechanical property tuning, achieving performances comparable to those of commercial plastics such as polystyrene, polymethyl methacrylate and polybutadiene. Techno-economic analysis and life cycle assessment for production at a scale of 100 kilotons per year show that the materials are currently slightly more expensive and environmentally intensive compared with conventional rubbers. However, use of recycled materials via depolymerization can greatly decrease the cost and environmental impacts of polymuconate production (for example, down to US$1.59 per kilogram) to outperform its commercial counterparts.

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

Using the Principals of Electrochemistry to Understand and Overcome the Complicated Degradation Mechanisms of Silicon Anodes in Lithium-Ion Batteries [Slides]

Battery technology is the most significant problem facing widespread market adoption of battery electric vehicles (BEVs). The low energy density of state-of-the-art lithium-ion electrode materials leaves BEV owners and prospective buyers with lower ranges than a comparable internal combustion engine (ICE) vehicle, and vulnerable to a nascent fast charging network. Silicon has the potential to increase the anode energy density by nearly ten times compared to the incumbent material (graphite) and make BEVs a more competitive transportation option. However, lithiated silicon is extremely reactive towards components of the electrolyte and forms a heterogeneous, complicated, and dynamic solid at its surface known as the solid electrolyte interphase (SEI). Ideally, the SEI would passivate the silicon surface, but continuous chemical degradation persists even when the battery is not operating. This reactivity reduces silicon anode lifetimes well below the necessary standards for BEVs. The NREL-led Silicon Consortium Project is dedicated to understanding and solving these mechanisms of degradation. Here, I will discuss an electrochemical method that provides deep insights into the silicon interface during battery operation. I will link these observations to fundamental electrochemical principals and how they translate into actionable strategies that extend the lifetime of silicon anodes.

25 ENERGY STORAGE↗
DOE OSTI2026

The structure, composition, and performance impact of a YSZ-GDC interdiffusion layer in solid oxide electrolysis cells

This study provides a combined experimental and computational investigation into the structure and impact of the cation interdiffusion layer that appears at the gadolinium doped ceria (GDC)/yttria stabilized zirconia (YSZ) interface in solid oxide electrolysis cells (SOECs). Scanning transmission electron microscopy (STEM) illustrates that a ∼0.4 μm interdiffusion layer (IDL) with an intermixed cation distribution and fine grain size forms upon sintering. STEM identifies that the interdiffusion layer exists in the cubic fluorite structure despite changes in cation composition. The interdiffusion layer microstructure formed during sintering does not change during SOEC testing at either 1.3V or heightened voltage pulse testing. Modeling predicts that ionic conductivity may decrease in the interdiffusion layer due to Coulombic trapping between mobile oxygen vacancies and excess Gd 3+ acceptor dopants. Yet, the density and continuous nature of the layer should benefit cell stability by substantially reducing the formation of SrZrO 3 , which is corroborated by STEM and Synchrotron X-ray diffraction (XRD). We conclude that the interdiffusion layer acts as a beneficial barrier to Sr diffusion, when operating in a regime where electrolyte void formation is not observed.

organic↗
DOE OSTI2025

Theoretical and Experimental Insights into CO 2 Capture and Methanation over Amine-Grafted Ru-Based Catalysts

Carbon capture and storage (CCS) technologies, along with CO 2 capture and conversion methods, have emerged as crucial research areas to address rising CO 2 emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO 2 conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO 2 into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO 2 methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO 2 conversion and CH 4 production rates over the synthesized catalysts “Ru/TiO 2 ” and the amine (N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO 2 ”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO 2 uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO 2 coverage at all temperatures. The MKM simulations consistently confirmed these trends. In conclusion, this comprehensive approach offers key insights into the role of the amine-CO 2 bond in methanation, highlighting a pathway toward lower-energy, more efficient CO 2 capture and conversion processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Role of Elemental Substitution on Hydrogen Incorporation in Characteristic Ti/Fe-Based Oxides

Elemental substitution is well-known to benefit hydrogen storage in the intermetallic compound TiFe; however, the impact of these substituents on the native and passivating surface oxide has not been well-established. Here, we perform density functional theory calculations on several characteristic oxides that are likely to form on exposed TiFe surfaces, specifically, TiO 2 , FeO, TiFeO 3 , and Ti 4 Fe 2 O. In TiO 2 and TiFeO 3 , additional acceptor species substituting for Ti can increase the solubility of protonic hydrogen (H i + ), likely enhancing hydrogen permeation of the oxide layer. In FeO, few dopants will act as acceptors, and hydrogen will incorporate as substitutional H O + , which is likely to be less mobile and will hinder hydrogen permeation. Finally, we find that Ti 4 Fe 2 O, which is thermodynamically metastable, may be stabilized by defects under O-poor conditions, although the presence of certain substitutional elements can destabilize it. In general, Mn, V, and Cr are among the best substituents for enhancing hydrogenation through the oxide layer. In conclusion, our results help to explain what features make additional elements particularly effective for enabling reversible hydrogen storage in TiFe, and they can guide further technological development of high-performing TiFe-based alloys for future energy applications.

organic↗
DOE OSTI2024

Functional roles of the [2Fe-2S] clusters in Synechocystis PCC 6803 Hox [NiFe]-hydrogenase reactivity with ferredoxins

The HoxEFUYH complex of Synechocystis PCC 6803 (S. 6803) consists of a HoxEFU ferredoxin:NAD(P)H oxidoreductase subcomplex and a HoxYH [NiFe]-hydrogenase subcomplex that catalyzes reversible H2 oxidation. Prior studies have suggested that the presence of HoxE is required for reactivity with ferredoxin; however, it is unknown how HoxE is functionally integrated into the electron transfer network of the HoxEFU:ferredoxin complex. Deciphering electron transfer pathways is challenged by the rich iron-sulfur cluster content of HoxEFU, which includes a [2Fe-2S] cluster in each subunit, along with multiple [4Fe-4S] clusters and a flavin cofactor. To resolve the role of HoxE, we determined the biophysical and thermodynamic properties of each [2Fe-2S] cluster in HoxEFU using steady-state and potentiometric EPR analysis in combination with square wave voltammetry (SWV). The temperature-dependence of the EPR signal for HoxE confirmed the coordination of a single [2Fe-2S] cluster that was shown by SWV to have an E m = -424 mV (versus SHE). Strikingly, when the E m of the HoxE [2Fe-2S] cluster was analyzed in HoxEFU titrations, it was shifted by >100 mV to an E m < -525 mV (versus SHE). EPR titrations of HoxEFU gave an E m value for the [2Fe-2S] cluster of HoxF, E m = -419 mV and HoxU, E m = -349 mV. These values were used to re-analyze the diaphorase kinetics in reactions performed with ferredoxins with varying E m 's. The results are formulated into a model of HoxEFU:ferredoxin reactivity and the role of HoxE in mediating electron transfer within the HoxEFU:ferredoxin complex.

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

Revealing CO 2 dissociation pathways at vicinal copper (997) interfaces

Size- and shape-tailored copper (Cu) nanocrystals can offer vicinal planes for facile carbon dioxide (CO 2 ) activation. Despite extensive reactivity benchmarks, a correlation between CO 2 conversion and morphology structure has not yet been established at vicinal Cu interfaces. Herein, ambient pressure scanning tunneling microscopy reveals step-broken Cu nanocluster evolutions on the Cu(997) surface under 1 mbar CO 2 (g). The CO 2 dissociation reaction produces carbon monoxide (CO) adsorbate and atomic oxygen (O) at Cu step-edges, inducing complicated restructuring of the Cu atoms to compensate for increased surface chemical potential energy at ambient pressure. The CO molecules bound at under-coordinated Cu atoms contribute to the reversible Cu clustering with the pressure gap effect, whereas the dissociated oxygen leads to irreversible Cu faceting geometries. Synchrotron-based ambient pressure X-ray photoelectron spectroscopy identifies the chemical binding energy changes in CO-Cu complexes, which proves the characterized real-space evidence for the step-broken Cu nanoclusters under CO(g) environments. Our in situ surface observations provide a more realistic insight into Cu nanocatalyst designs for efficient CO 2 conversion to renewable energy sources during C 1 chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Pattern-enhanced Resonant Soft X-ray Scattering for Operando monitoring of electrochemical solid-liquid interfaces

Unveiling interfaces at sub-nanometer scales is essential for advancing the understanding of complex chemical transformations. However, characterizing solid-liquid interfaces with high dimensional sensitivity and temporal resolution remains challenging, due to their dynamic nature and inaccessibility by conventional probes. Here we present an approach, Pattern-enhanced Resonant Soft X-ray Scattering, to overcome the challenges. Rooted in a “sample-as-optics” philosophy, this technique utilizes precisely engineered line-grating nanopatterns to modulate near-field X-ray illumination, coherently enhancing scattering signals from the line-gratings. We implement the method using Ni line-grating nanopatterns in electrochemical water oxidation. The periodic nanostructures serve as diffractive optical elements to reveal the Ni oxidation gradients and structural dynamics at the electrode-electrolyte interfaces. Finite-element simulations corroborate the observed trends by modeling variations in compositions and structures during electrocatalysis. Through integrating advanced sample design with coherent wave nature of soft X-rays, our approach opens accessible pathways to operando exploring chemical evolution and sub-nanometer dimensional variations simultaneously in electrochemical systems. This non-destructive method is efficient and element-specific, making it valuable for probing chemical and dimensional dynamics with appropriate modeling.

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

Nanofabrication of synthetic nanoporous geomaterials: from nanoscale-resolution 3D imaging to nano-3D-printed digital (shale) rock

Abstract Advances in imaging have made it possible to view nanometer and sub-nanometer structures that are either synthesized or that occur naturally. It is believed that fluid dynamic and thermodynamic behavior differ significantly at these scales from the bulk. From a materials perspective, it is important to be able to create complex structures at the nanometer scale, reproducibly, so that the fluid behavior may be studied. New advances in nanoscale-resolution 3D-printing offer opportunities to achieve this goal. In particular, additive manufacturing with two-photon polymerization allows creation of intricate structures. Using this technology, a creation of the first nano-3D-printed digital (shale) rock is reported. In this paper, focused ion beam-scanning electron microscopy (FIB-SEM) nano-tomography image dataset was used to reconstruct a high-resolution digital rock 3D model of a Marcellus Shale rock sample. Porosity of this 3D model has been characterized and its connected/effective pore system has been extracted and nano-3D-printed. The workflow of creating this novel nano-3D-printed digital rock 3D model is described in this paper.

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

Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface

The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO 2 -to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here, in this work, we utilize in situ infrared nanospectroscopy and surface-enhanced Raman spectroscopy, unveiling an electrochemical bias-induced consecutive bond cleavage mechanism of surface ligands leading to formation of the NP/ordered-ligand interlayer. This real-time molecular insight could influence the design of confined localized fields in multiple catalytic systems. Moreover, the demonstrated capability of capturing nanometre-resolved, dynamic molecular-scale events holds promise for the advancement of using controlled local molecular behaviour to achieve desired functionalities across multiple research domains in nanoscience.

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

Glycosyltransferase family 47 (GT47) proteins in plants and animals

Glycosyltransferases (GTs) are carbohydrate-active enzymes that are encoded by the genomes of organisms spanning all domains of life. GTs catalyze glycosidic bond formation, transferring a sugar monomer from an activated donor to an acceptor substrate, often another saccharide. GTs from family 47 (GT47, PF03016) are involved in the synthesis of complex glycoproteins in mammals and insects and play a major role in the synthesis of almost every class of polysaccharide in plants, with the exception of cellulose, callose, and mixed linkage β-1,3/1,4-glucan. GT47 enzymes adopt a GT-B fold and catalyze the formation of glycosidic bonds through an inverting mechanism. Unlike animal genomes, which encode few GT47 enzymes, plant genomes contain 30 or more diverse GT47 coding sequences. With our current knowledge of the GT47 family across plant species brings us an interesting view, showcasing how members exhibit a great diversity in both donor and acceptor substrate specificity, even for members that are classified in the same phylogenetic clade. Thus, we discuss how plant GT47 family members represent a great case to study the relationship between substrate specificity, protein structure, and protein evolution. Most of the plant GT47 enzymes that are identified to date are involved in biosynthesis of plant cell wall polysaccharides, including xyloglucan, xylan, mannan, and pectins. This indicates unique and crucial roles of plant GT47 enzymes in cell wall formation. The aim of this review is to summarize findings about GT47 enzymes and highlight new challenges and approaches on the horizon to study this family.

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

The presence and role of the intermediary CO reservoir in heterogeneous electroreduction of CO 2

Significance The electroconversion of CO 2 to value-added products is a promising path to sustainable fuels and chemicals. However, the microenvironment that is created during CO 2 electroreduction near the surface of heterogeneous Cu electrocatalysts remains unknown. Its understanding can lead to the development of ways to improve activity and selectivity toward multicarbon products. This work introduces a method called on-stream substitution of reactant isotope that provides quantitative information of the CO intermediate species present on Cu surfaces during electrolysis. An intermediary CO reservoir that contains more CO molecules than typically expected in a surface adsorbed configuration was identified. Its size was shown to be a factor closely associated with the formation of multicarbon products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗