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Results for “Reaction mechanism”

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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Hydration and reaction mechanisms on sodium silicate glass surfaces from molecular dynamics simulations with reactive force fields

Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. Furthermore, we have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Highly selective Si 3 N 4 /SiO 2 etching using an NF 3 /N 2 /O 2 /H 2 remote plasma. II. Surface reaction mechanism

Developing processes for highly selective etching of silicon nitride (Si 3 N 4 ) with respect to silicon dioxide (SiO 2 ) is a major priority for semiconductor fabrication processing. In this paper and in Paper I [Volynets et al., J. Vac. Sci. Technol. A 38, 023007 (2020)], mechanisms are discussed for highly selective Si3N4 etching in a remote plasma based on experimental and theoretical investigations. The Si 3 N 4 /SiO 2 etch selectivity of up to 380 was experimentally produced using a remote plasma sustained in NF 3 /N 2 /O 2 /H 2 mixtures. A selectivity strongly depends on the flow rate of H 2 , an effect attributed to the formation of HF molecules in vibrationally excited states that accelerate etching reactions. Based on experimental measurements and zero-dimensional plasma simulations, an analytical etching model was developed for etch rates as a function of process parameters. Reaction rates and sticking coefficients were provided by quantum chemistry models and also fitted to the experimental results. Etch rates from the analytical model show good agreement with the experimental results and demonstrate why certain etchants accelerate or inhibit the etch process. In particular, the modeling shows the important role of HF molecules in the first vibrationally excited state [HF( v = 1)] in achieving high Si 3 N 4 /SiO 2 selectivity.

42 ENGINEERING↗
DOE OSTI2025

Hydrothermal Liquefaction of Structurally Diverse Lignins: Insights into Biocrude Yield, Fuel Properties, and Reaction Mechanisms

Lignin holds significant promise as a feedstock for biocrude production via hydrothermal liquefaction (HTL). Although lignin HTL has been widely studied, the specific depolymerization pathways associated with distinct lignin structures remain largely unexplored. This study investigates the HTL of four structurally diverse lignins: alkaline (AL), dealkaline (DAL), organosolv (OL), and lignosulfonate (LS) across 270–310 °C to elucidate structure-specific mechanisms governing biocrude yield and composition. AL and OL achieved the highest yields (16.8 ± 0.3% and 16.8 ± 2.5%), with AL-derived biocrude showing the highest carbon content (70.2 ± 0.0%) and HHV (31.0 ± 0.2 MJ/kg). In contrast, DAL and LS produced lower yields and inferior fuel quality due to higher sulfur content and lower carbon enrichment. The structures of AL and DAL, containing fewer methoxy groups, produced guaiacol-rich biocrudes (46.6% and 69.5%). Methylation in AL formed alkyl guaiacols and veratroles, while DAL favored side-chain oxidation. OL retained complex structures, forming syringols and desaspidinol, which contributed to heavier biocrude compounds. Sulfonate groups in LS were stabilized mostly as sulfides, leading to elevated sulfur content. These findings provide mechanistic insight into how lignin structure governs HTL behavior, enabling targeted control of biocrude yield and quality for renewable fuel production.

biocrude↗
DOE OSTI2025

Alpha ketoacid decarboxylases: Diversity, structures, reaction mechanisms, and applications for biomanufacturing of platform chemicals and fuels

In living cells, alpha-ketoacid decarboxylases (KDCs, EC 4.1.1.-) are a class of enzymes that convert alpha-ketoacids into aldehydes through decarboxylation. These aldehydes serve as either drop-in chemicals or precursors for the biosynthesis of alcohols, carboxylic acids, esters, and alkanes. These compounds play crucial roles in cellular metabolism and fitness and the bioeconomy, facilitating the sustainable and renewable biomanufacturing of platform chemicals and fuels. This review explores the diversity and classification of KDCs, detailing their structures, mechanisms, and functions. We highlight recent advancements in repurposing KDCs to enhance their efficiency and robustness for biomanufacturing. Additionally, we present modular KDC-dependent metabolic pathways for the microbial biosynthesis of aldehydes, alcohols, carboxylic acids, esters, and alkanes. Lastly, we discuss recent developments in the modular cell engineering technology that can potentially be applied to harness the diversity of KDC-dependent pathways for biomanufacturing platform chemicals and fuels.

09 BIOMASS FUELS↗
DOE OSTI2025

Reaction Mechanism of the Synthesis of a Disordered Rock Salt Cathode Material

Li-rich disordered rock salt (DRX) materials have recently emerged as a class of promising cathode materials for cobalt- and nickel-free Li-ion batteries that can achieve a high energy density and high electrochemical storage capacity. Here, the synthesis conditions of DRX were found to have a significant impact on the electrochemical performance of the final product formed and hence need to be carefully controlled. To date, the formation pathway of DRX materials has remained largely unexplored. In this work, the phase evolution of a DRX material, Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 (LMTF1811), during solid-state synthesis, was monitored using in situ synchrotron X-ray diffraction (sXRD). We have observed several crystalline intermediates formed during the synthesis process before the full formation of DRX. Ex situ X- ray absorption spectroscopy (XAS) was used to assess the local structure and charge states of the transition metals. F K-edge XAS collected from the final product LMTF1811 shows that the degree of F incorporation into the DRX phase is low.

Diffraction↗
DOE OSTI2025

Tuning the Molecular Structure and Reaction Mechanism of Olefin Metathesis by Model Bilayered Supported MoO x /AlO x /SiO 2 Catalysts

The molecular structure and activity of supported MoO x olefin metathesis catalysts are heavily impacted by the choice of catalyst support. In this study, surface modification of the SiO 2 support with AlO x and selective anchoring of the MoO x on the surface AlO x sites were used to tune the structure, activation, and reactivity of the resulting surface MoO x sites. Extensive in situ molecular characterization, chemical probe studies, and density functional theory (DFT) calculations reveal that the enhanced activity of the supported MoO x /AlO x /SiO 2 catalyst over the MoO x / SiO 2 catalyst is associated with more favorable activation and kinetics of surface MoO x anchored at AlO x sites.

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

Modeling an S N 2 Reaction Mechanism for Hydrolysis of Siloxane Linkages with Density Functional Theory under Basic Conditions and Implications for Dissolution of Quartz

An extended silicate molecular cluster was used to perform density functional theory calculations to determine if an S N 2 mechanism, where OH – attacks a Q 1 Si coupled with Na + charge balancing an adjacent siloxane bridging O atom, could explain the observed energy of activation of quartz dissolution under basic conditions.

chemical calculations↗