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Results for “scaling reactions”

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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Developing a new ethylene glycol/H 2 O pretreatment system to achieve efficient enzymatic hydrolysis of sugarcane bagasse cellulose and recover highly active lignin: Countercurrent extraction

Improving pretreatment efficiency is a critical premise in achieving efficient biomass conversion, and obtaining high-performance natural polymers is the guarantee of high-value conversion of biomass. Here, in this study, a new pilot-scale continuous countercurrent pretreatment reaction unit about ethylene glycol-alkali solution was designed for pretreating sugarcane bagasse in order to achieve efficient separation of the three major components of lignocellulose when expanding the scale of pretreatment, reduce lignin deposition on the fiber surface, and obtain highly active lignin and excellent enzymatic hydrolysis efficiency of cellulose. X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS), brunauer-emmett-teller (BET) and scanning electron microscope (SEM) methods are used to analyze the structural properties of sugarcane bagasse before and after pretreatment, and high-performance liquid chromatography (HPLC) is used to analyze the monosaccharide components in the enzymatic solution. In addition, the structural properties of the recovered lignin are analyzed by gel permeation chromatography (GPC), 31 P NMR and 2D-HSQC-NMR methods. The results indicate that the system can gain a high cellulose recovery of 92.99% along with a lignin removal of 95.33%, and recovered lignin has low lignin carbohydrate complexes, low condensation, and rich in phenolic hydroxyl groups for 1.95 mmol/g. Meanwhile, the countercurrent pretreatment system can effectively reduce the deposition of lignin on the cellulose surface, which is evidently superior to the non-countercurrent pretreatment and facilitates the efficiency of enzymatic saccharification of substrate, achieving a high glucose yield of 99% as well as a total sugar yield of 91.11%. The method efficiently separates biomass in a green manner, and solid residues are easily hydrolyzed, showing potential for industrial-scale production.

09 BIOMASS FUELS↗
DOE OSTI2026

A photochargeable semiconductor for highly efficient dehydrogenative coupling of amines

The development of materials with high photocatalytic efficiency is essential for sustainable chemical transformations. Here, in this work, we introduce photochargeable zinc indium sulfide nanocrystals with notable charge storage capacity, enabling highly efficient photocatalytic dehydrogenative coupling of amines. Combined with a nickel cocatalyst, the nanocrystals deliver diamines and hydrogen at rates exceeding 120 mmol per gram of photocatalyst per hour, with > 95% selectivity and an apparent quantum efficiency of up to 39.4% under ambient conditions. The system exhibits excellent scalability, demonstrated by a reaction on a 20-g scale, and broad versatility in promoting amino acid ester coupling and polymerization reactions with concurrent hydrogen evolution. Mechanistic studies attribute the photocharging capability of zinc indium sulfide nanocrystals to in situ-generated trap states such as sulfur vacancies, which extend hydrogen production into the dark catalytic cycle and enhance the overall charge utilization efficiency. These findings position photochargeable semiconductors as promising platforms for a wide range of photocatalytic applications.

nanoscale devices↗
DOE OSTI2025

Resolving electrochemically triggered topological defect dynamics and structural degradation in layered oxides

Understanding topological defects-controlled structural degradation of layered oxides—a key cathode material for high-performance lithium-ion batteries—plays a critical role in developing next-generation cathode materials. Here, by constructing a nanobattery in an electron microscope enabling atomic-scale monitoring of electrochemcial reactions, we captured the electrochemically driven atomistic dynamics and evolution of dislocations—a most important topological defect in material. We deciphered how dislocations nucleate, move, and annihilate within layered cathodes at the atomic scale. Specifically, we found two types of dislocation configurations, i.e., single dislocations and dislocation dipoles. Both pure dislocation glide/climb and mixed motions were captured, and the dislocation glide and climb velocities were first experimentally measured. Moreover, dislocation activity-mediated structural degradation such as crack nucleation, phase transformation, and lattice reorientation was unraveled. Our work provides deep insights into the atomistic dynamics of electrochemically driven dislocation activities in layered oxides.

Wang, Chunyang (ORCID:0000000184613952)↗
DOE OSTI2022

Molecular-scale mechanisms of CO 2 mineralization in nanoscale interfacial water films

The calamitous impacts of untethered carbon emission from fossil-fuel-burning energy infrastructure calls for accelerated development of large-scale CO 2 capture, utilization, and storage technologies that are underpinned by fundamental understanding of molecular-level chemical processes. In the subsurface, rocks rich in divalent metals can react with CO 2 , permanently sequestering it in the form of stable metal carbonate minerals, with the CO 2 -H 2 O composition of the post-injection pore fluid acting as a primary control variable. Herein, we compare mechanistic reaction pathways for aqueous-mediated carbonation with carbon mineralization occurring in nanoscale adsorbed water films. In the extreme of pores filled with a CO 2 -dominant fluid, carbonation reactions are confined to nanometer-thick water films coating mineral surfaces, which enable metal cation release, transport, nucleation, and crystallization of metal carbonate minerals. Though seemingly counterintuitive, laboratory studies have demonstrated facile carbonation rates in these low water environments, which in recent years has begun to be better understood in mechanistic detail. The overarching objective of this review is to delineate the unique underlying molecular-scale reaction mechanisms that govern CO 2 mineralization in these reactive and dynamic quasi-2D interfaces. Here. we highlight the importance of understanding unique properties in thin water films, such as how water dielectric properties, and consequently ion solvation/hydration behavior, can change under nanoconfinement. We conclude by identifying important frontiers for future work and opportunities to exploit these fundamental chemical insights for decarbonization technologies in the 21st century.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Defect-driven selective metal oxidation at atomic scale

Nanoscale materials modified by crystal defects exhibit significantly different behaviours upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However, unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale remains a challenge for applications. Here, using in situ high-resolution transmission electron microscopy and first-principles calculations, we reveal the dynamics of a general site-selective oxidation behaviour in nanotwinned silver and palladium driven by individual stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit the highest oxygen binding energies, leading to preferential nucleation of oxides at these intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse subsequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal interface. These findings provide an atomistic visualization of the complex reaction dynamics controlled by planar defects in metallic nanostructures, which could enable the modification of physiochemical performances in nanomaterials through defect engineering.

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

DNA Reaction–Diffusion Attractor Patterns

Living systems can form and recover complex chemical patterns with precisely sized features in the ranges of tens or hundreds of microns. We show how designed reaction-diffusion processes can likewise produce precise patterns, termed attractor patterns, that reform their precise shape after being perturbed. We use oligonucleotide reaction networks, photolithography and microfluidic delivery to form precisely controlled attractor patterns and study the responses of these patterns to different localized perturbations. Linear and ‘hill’-shaped patterns formed and stabilized into shapes and at time scales consistent with reaction-diffusion models. When patterns were perturbed in particular locations with UV light, they reliably reformed their steady state profiles. Recovery also occurred after repeated perturbations. As a result, by designing the far-from-equilibrium dynamics of a chemical system, this study shows how it is possible to design spatial patterns of molecules that are sustained and regenerated by continually evolving towards a specific steady state configuration

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

Investigating Gas Dynamics and Reactions in Supersonic Jets

UF6 is highly reactive and readily hydrolyzes in contact with moisture to form uranyl fluoride (UO2 F2 ) and hydrofluoric acid (HF), however there is disagreement between experimental and computation investigations into the intermediates of the reaction. • As the hydrolysis reaction occurs at very fast time scales, it is difficult to investigate the intermediates and reaction kinetics experimentally. • Previous experiments at SRNL have had some success at halting and studying the UF6 hydrolysis reaction using cryogenic techniques, however isotopic substitution studies limit possible identity of intermediate compounds. • Primary goal of this project is to capture and study reaction intermediates produced during the gas phase hydrolysis of UF6 via supersonic expansion.

Waldron, Abigail M.↗
DOE OSTI2021

Recent advances in nano-scale spatial resolution x-ray microscopy instrumentation at NSLS-II

X-ray microscopy is an invaluable and powerful characterization tool applied in many scientific fields, such as materials science, biology, environmental science, and energy research. In recent years it has been driven by rapid developments of novel technologies and systems resulting in imaging experiments elucidating structural inhomogeneities and chemical reactions at the nanometer scale. To obtain high spatial resolution comprehensive chemical and structural information, an X-ray microscope must be equipped with adequate capabilities and allow for simultaneous acquisition of multiple datasets. In recent years, a number of X-ray microscopes have been designed, constructed, and commissioned at NSLS-II. Here we provide an overview of the microscopy instrumentation development program at NSLS-II and specifically focus on the multilayer Laue lens-based hard X-ray nanoprobe optimized for ~10 nm spatial resolution imaging, its current status, and future upgrades along with recently constructed Kirkpatrick-Baez based scanning microscope designed for ~100 nm spatial resolution experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Path to Increasing p-B11 Reactivity via ps and ns Lasers

The Lawson criterion for proton-boron (p-11B) thermonuclear fusion is substantially higher than that for deuterium-tritium (DT) because the fusion cross section is lower and peaks at higher ion energies. The Maxwellian averaged p-11B reactivity peaks at several hundred keV, where bremsstrahlung radiation emission may dominate over fusion reactions if electrons and ions are in thermal equilibrium and the losses are unrestricted. Nonequilibrium burn has often been suggested to realize the benefits of this aneutronic reaction, but the predominance of elastic scattering over fusion reactivity makes this difficult to achieve. The development of ultrashort pulse lasers (USPL) has opened new possibilities for initiating nonequilibrium thermonuclear burns and significant numbers of p-11B alpha particles have been reported from several experiments. We present an analysis that shows that these significant alpha yields are the result of beam fusion reactions that do not scale to net energy gain. We further find that the yields can be explained by experimental parameters and recently updated cross sections such that a postulated avalanche mechanism is not required. We use this analysis to understand the underlying physics of USPL-driven nonequilibrium fusion reactions and whether they can be used to initiate fusion burns. We conclude by outlining a path to increasing the p-11B reactivity towards the goal of achieving ignition and describing the design principles that we will use to develop a computational point design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Evolution of the Rate-Limiting step: From Thin Film to Thick Ni-rich Cathodes

Ni-rich NMC (LiNixMnyCo1-x-yO2, x = 0.6) has the attributes of high specific capacity (greater than 180 mAh g-1), high operating voltage (ca. 3.8 V) and low cost, which is therefore deemed as one of the most promising cathode candidates for next-generation high-energy Li-ion batteries (LIBs). However, challenges exist before the large-scale commercialization of Ni-rich cathode such as gas generation, capacity degradation especially at high rate or elevated temperatures. From thin film to densely pack high loading cathode, this work investigates the rate-limiting steps in Ni-rich cathodes e.g., phase structure, electronic and ionic conductivity to understand the reaction kinetics at different scales. This work provides new insights in understanding the electrochemical properties of Ni-rich cathode at different levels to inspire revolutionary ideas to address the fundamental issues of Ni-rich cathode from materials to relevant electrode levels.

Hu, Jiangtao↗
DOE OSTI2024

Parametric tuning of quantum phase transitions in ultracold reactions

Advances in atomic physics have led to the possibility of a coherent transformation between ultracold atoms and molecules including between completely bosonic condensates. Such transformations are enabled by the magneto-association of atoms at a Feshbach resonance which results in a passage through a quantum critical point. In this study, we show that the presence of generic interaction between the constituent atoms and molecules can fundamentally alter the nature of the critical point, change the yield of the reaction and the order of the consequent phase transition. We find that the correlations introduced by this interaction induce nontrivial many-body physics such as coherent oscillations between atoms and molecules, and a selective formation of squeezed molecular quantum states and quantum cat states. We provide analytical and numerical descriptions of these effects, along with scaling laws for the reaction yield in non-adiabatic regimes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Atomic-scale insights into topotactic transformations in an extra-large-pore zeolite using time-resolved 3D electron diffraction

Understanding the atomic-scale structural dynamics of phase transformations is crucial for developing materials and tailoring their properties. However, many materials are obtained as polycrystalline powders with large unit cells and/or complex structures, making it challenging to investigate detailed structural changes using conventional X-ray diffraction techniques. Here we employ time-resolved three-dimensional electron diffraction to reveal the topotactic reactions and transformations that convert the extra-large-pore silicate zeolite ECNU-45 into ECNU-46. ECNU-45 features three-dimensional interconnecting 24 × 10 × 10-ring channels, while ECNU-46 consists of one-dimensional 24-ring channels connected to 10-ring pockets. ECNU-45 and ECNU-46 are both examples of pure silicate zeolites with pore openings larger than 22-ring. Our findings indicate changes at six distinct tetrahedral silicon sites, involving atom displacement, addition and removal of framework atoms through bond breakage and formation. This work presents the synthesis of zeolites and also provides atomic-level insights into the dynamic processes of topotactic reactions. Our results have implications for advancing materials engineering and understanding complex solid-state reactions at an atomic scale.

Inorganic chemistry↗
DOE OSTI2020

A parameter sensitivity study for simulating DNA damage after proton irradiation using TOPAS-nBio

Monte Carlo (MC) track structure simulation tools are commonly used for predicting radiation induced DNA damage by modeling the physical and chemical reactions at the nanometer scale. However, the outcome of these MC simulations is particularly sensitive to the adopted parameters which vary significantly across studies. In this study, a previously developed full model of nuclear DNA was used to describe the DNA geometry. The TOPAS-nBio MC toolkit was used to investigate the impact of physics and chemistry models as well as three key parameters (the energy threshold for direct damage, the chemical stage time length, and the probability of damage between hydroxyl radical reactions with DNA) on the induction of DNA damage. Our results show that the difference in physics and chemistry models alone can cause differences up to 34% and 16% in the DNA double strand break (DSB) yield, respectively. Additionally, changing the direct damage threshold, chemical stage length, and hydroxyl damage probability can cause differences of up to 28%, 51%, and 71% in predicted DSB yields, respectively, for the configurations in this study.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Mechanical and Light Activation of Materials for Chemical Production

Abstract Mechanical expansion and contraction of pores within photosynthetic organisms regulate a series of processes that are necessary to manage light absorption, control gas exchange, and regulate water loss. These pores, known as stoma, allow the plant to maximize photosynthetic output depending on environmental conditions such as light intensity, humidity, and temperature by actively changing the size of the stomal opening. Despite advances in artificial photosynthetic systems, little is known about the effect of such mechanical actuation in synthetic materials where chemical reactions occur. It is reported here on a hybrid hydrogel that combines light‐activated supramolecular polymers for superoxide production with thermal mechanical actuation of a covalent polymer. Superoxide production is important in organic synthesis and environmental remediation, and is a potential precursor to hydrogen peroxide liquid fuel. It is shown that the closing of pores in the hybrid hydrogel results in a substantial decrease in photocatalysis, but cycles of swollen and contracted states enhance photocatalysis. The observations motivate the development of biomimetic photosynthetic materials that integrate large scale motion and chemical reactions.

Đorđević, Luka [Department of Chemical Sciences Un↗
DOE OSTI2024

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO 2 , H 2 O, and O 2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. Here, the emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

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

Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities” such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide– and silicate–water interfaces. This critical review discusses how science progresses from understanding ideal solid–water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. Further, we anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗