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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

On the Mechanism of Soot Nucleation. III. The Fate and Facility of the E-Bridge

Rotationally-excited dimerization of aromatic moieties is a mechanism proposed recently to explain the initial steps of soot particle inception in combustion and pyrolysis of hydrocarbons. The product of such dimerization, termed E-bridge, is an angled molecular structure composed of two aromatic rings sharing a common bond. The present study explores the immediate fate of the E-bridge. The performed theoretical analysis indicates that abstraction of a bridge H atom by a gaseous H leads to a rapid transformation of the angled to planar structure. The implications of this result is that the collisionally-activated E-bridge formation followed by its flattening effectively increases the size of “planar” aromatic precursors by combining two aromatic moieties with essentially collisional rates, instead of a slower “atom-by-atom” buildup. The faster growth speeds up PAH reaching a size when physical dimerization takes over. Furthermore, the dimerization can be further assisted by the biradicaloid valence structure of the flattened E-bridge.

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

Covalent Triazine Framework-Derived Membranes: Engineered Sol–Gel Construction and Gas Separation Application

Covalent triazine frameworks (CTFs) represent one of the most extensively studied organic networks characterized by graphitic π-conjugated structures linked by aza-fused rings, possessing unique features such as compositions of light elements (e.g., C, H, and N), porous architectures abundant heteroatom involvement, and extensively conjugated structures. In addition, the textural and chemical structures of CTFs could be engineered via synthesis control to accommodate diverse applications. CTF materials with notable characteristics, including plentiful (ultra-)micropores, high surface areas, and the presence of CO 2 -philic functional groups involving nitrogen (N), oxygen (O), and fluorine (F), hold great promise as potential candidates for anthropogenic CO 2 capture and sequestration (CCS) applications. However, the conventional high-temperature involved ionothermal procedures and the solution-based coupling pathway only afforded CTF materials in powder form, which is difficult to be processed toward membrane formation. Successful fabrication of CTF-derived membranes will rely on the development of alternative polymerization approaches as well as structural engineering to afford membrane architectures with controllable porosity distribution and active interaction sites with CO 2 benefiting the CO 2 separation procedure. In this Account, a demonstration of the latest progress in the development of CTF-derived membranes was provided. The CTF membranes were mainly synthesized via a superacid (e.g., CF 3 SO 3 H)-promoted sol–gel approach involving the polymerization of aromatic nitrile monomers. The formation of the triazine unit through the trimerization of cyano groups served as the cross-linkers, resulting in the creation of π-conjugated networks alongside the arenes present in the starting materials. The aromatic nitrile monomers with rigid and sterically hindered structures were required to afford CTF membranes with nanoporous architectures. The acidity of the superacid and reactivity of the aromatic monomers played critical roles in the polymerization efficiency. The monomer diversity and synthesis tunability endowed the introduction of CO 2 -philic functionalities (e.g., pyrazole and fluorine) within the CTF skeletons, and integration of ionic moieties was achieved by adopting FSO 3 H with stronger acidity as the catalyst and aromatic nitrile monomers with pyrazine structures. To ensure the successful construction of fluorinated CTF membranes, it is important to avoid any fluorines on the ortho-position of the cyano groups on the benzene ring. Through control over the monomers and reaction conditions, flexible, transparent, and insoluble CTF membranes could be fabricated. The sol–gel method could be further expanded to membrane fabrication through acetyl-to-benzene transformation through synthesis control. The mild oxidation-exfoliation-filtration method was also demonstrated to fabricate substrate-supported CTF membranes. The as-afforded membranes are well characterized to determine the structural features and provide information to study the structure-performance relationship. Here, the application of CTF membranes in CO 2 separation was summarized, focusing on the approaches being developed to enhance CO 2 uptake and separation performance. In addition to utilizing the pristine CTF membranes for gas separation, functionalized carbon molecular sieve membranes could be obtained from the pyrolysis of thermally stable CTF membrane precursors toward efficient CO 2 separation, benefiting from the abundant ultramicropores being created during the pyrolysis/decomposition procedure and involvement of CO 2 -philic functionalities such as fluorine and nitrogen-containing moieties. Based on these achievements, unsolved issues in CTF membrane-related fabrication and applications, including the potential solution approaches, have been proposed to advance the application of CTF membranes.

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

Polarimetric Geometric Modeling for mm-VLBI Observations of Black Holes

The Event Horizon Telescope (EHT) is a millimeter very long baseline interferometry (VLBI) array that has imaged the apparent shadows of the supermassive black holes M87* and Sagittarius A*. Polarimetric data from these observations contain a wealth of information on the black hole and accretion flow properties. In this work, we develop polarimetric geometric modeling methods for mm-VLBI data, focusing on approaches that fit data products with differing degrees of invariance to broad classes of calibration errors. We establish a fitting procedure using a polarimetric “m-ring” model to approximate the image structure near a black hole. By fitting this model to synthetic EHT data from general relativistic magnetohydrodynamic models, we show that the linear and circular polarization structure can be successfully approximated with relatively few model parameters. We then fit this model to EHT observations of M87* taken in 2017. In total intensity and linear polarization, the m-ring fits are consistent with previous results from imaging methods. In circular polarization, the m-ring fits indicate the presence of event-horizon-scale circular polarization structure, with a persistent dipolar asymmetry and orientation across several days. The same structure was recovered independently of observing band, used data products, and model assumptions. Despite this broad agreement, imaging methods do not produce similarly consistent results. Our circular polarization results, which imposed additional assumptions on the source structure, should thus be interpreted with some caution. Polarimetric geometric modeling provides a useful and powerful method to constrain the properties of horizon-scale polarized emission, particularly for sparse arrays like the EHT.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Competition between Water–Water Hydrogen Bonds and Water–π Bonds in Pyrene–Water Cluster Anions

We present infrared spectra and density functional theory calculations of hydrated pyrene anion clusters with up to four water molecules. The experimental spectra were acquired using infrared Ar messenger photodissociation spectroscopy. Water molecules form clusters on the surface of the pyrene, forming hydrogen bonds with the pi-system. The structures of the water clusters and their interaction with the π-system are encoded in the OH stretching vibrational modes. Here, we find that the interactions between water molecules are stronger than they are between water molecules and the π-system. While all clusters show multiple conformers, three- and four-membered rings are the lowest energy structures in the larger hydrates.

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

Composition and Structure of Fluorescent Graphene Quantum Dots Generated by Enzymatic Degradation of Graphene Oxide

The broad applications of carbon nanomaterials (CNMs) in both materials and life sciences necessitate investigation of their metabolites due to the inevitable contact of CNMs and biological systems. Graphene oxide (GO), along with other types of CNMs, can be enzymatically degraded by myeloperoxidase (MPO), an enzyme released during the innate immune response. However, the enzymatic degradation products are neither well-defined nor well-understood. Some products generated during MPO-catalyzed degradation of GO could emit blue photoluminescence (PL) and were simply dubbed graphene quantum dots (GQDs) without further elucidating their structures. In this work, we use liquid chromatography-mass spectrometry (LC-MS) to isolate and elucidate chemical structures of the MPO-catalyzed degradation products. A general chemical formula screening workflow was developed for the GQDs, which are in the form of polyaromatic hydrocarbons (PAHs), obtained in the degradation products. Structures of the PAHs responsible for the blue PL were further proposed using density functional theory (DFT) calculations. Our results indicated that structures with several conjugated benzene rings are likely to generate the observed PL. This work provides insights into the mechanism of enzymatic degradation and open opportunities for fluorescence imaging of GO in biological systems.

composition and structure screening↗
DOE OSTI2023

Aminobenzoic Acid Derivatives Obstruct Induced Fit in the Catalytic Center of the Ribosome

The Escherichia coli (E. coli) ribosome can incorporate a variety of non-l-α-amino acid monomers into polypeptide chains in vitro but with poor efficiency. Although these monomers span a diverse set of compounds, there exists no high-resolution structural information regarding their positioning within the catalytic center of the ribosome, the peptidyl transferase center (PTC). Thus, details regarding the mechanism of amide bond formation and the structural basis for differences and defects in incorporation efficiency remain unknown. Within a set of three aminobenzoic acid derivatives–3-aminopyridine-4-carboxylic acid (Apy), ortho-aminobenzoic acid (oABZ), and meta-aminobenzoic acid (mABZ)–the ribosome incorporates Apy into polypeptide chains with the highest efficiency, followed by oABZ and then mABZ, a trend that does not track with the nucleophilicity of the reactive amines. Here, we report high-resolution cryo-EM structures of the ribosome with each of these three aminobenzoic acid derivatives charged on tRNA bound in the aminoacyl-tRNA site (A-site). The structures reveal how the aromatic ring of each monomer sterically blocks the positioning of nucleotide U2506, thereby preventing rearrangement of nucleotide U2585 and the resulting induced fit in the PTC required for efficient amide bond formation. They also reveal disruptions to the bound water network that is believed to facilitate formation and breakdown of the tetrahedral intermediate. Together, the cryo-EM structures reported here provide a mechanistic rationale for differences in reactivity of aminobenzoic acid derivatives relative to l-α-amino acids and each other and identify stereochemical constraints on the size and geometry of non-monomers that can be accepted efficiently by wild-type ribosomes.

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

How do substituted phenyl-based cations affect the structure-property-stability relationship of low-dimensional perovskites?

Incorporating organic bulky cations in the precursor or post-treatment to achieve two-dimensional/three-dimensional (2D/3D) heterojunction is an effective strategy for enhancing the stability of perovskite materials. However, the issue of insufficient charge transport in 2D perovskites limits their development, and the fundamental mechanism of out-of-plane carrier transport remains unclear. This study designed and synthesized seven organic phenyl-core cations, differentiated at the 1- and 1,4-positions, and identified the impacts on the corresponding properties of the 2D crystalline perovskite. Shorter cations facilitated a more compact arrangement of adjacent inorganic layers, aligning to favor charge transport along the vertical direction. In addition, introducing high electronegativity led to increased intermolecular interactions, resulting in enhanced structural stability and improved phenyl ring π-orbital overlap and interlayer electron coupling, yielding efficient charge transport. Resilience to thermal stressing of the perovskite was strongly correlated with the carbon chain length of the spacer cations. Here, the increase in cation length and the reduction in the rigidity of the amino-terminal both aided in the dispersion of thermal stress in the inorganic framework. Additional hydrogen bonding also contributed to mitigating structural disorder.

14 SOLAR ENERGY↗
DOE OSTI2022

The Milky Way’s middle-aged inner ring

Aims. We investigate the metallicity, age, and orbital anatomy of the inner Milky Way, specifically focussing on the outer bar region. Methods. We integrated a sample of APOGEE DR16 inner Galaxy stars in a state of the art bar-bulge potential with a slow pattern speed and investigated the link between the resulting orbits and their [Fe/H] and ages. By superimposing the orbits, we built density, [Fe/H], and age maps of the inner Milky Way, which we divided further using the orbital parameters eccentricity, |Xmax|, and |Zmax|. Results. We find that at low heights from the Galactic plane, the Galactic bar gradually transitions into a radially thick, vertically thin, elongated inner ring with average solar [Fe/H]. This inner ring is mainly composed of stars with AstroNN ages between 4 and 9 Gyr with a peak in age between 6 and 8 Gyr, making the average age of the ring ~6 Gyr. The vertical thickness of the ring decreases markedly towards younger ages. We also find very large L4 Lagrange orbits that have average solar to super-solar metallicities and intermediate ages. Lastly, we confirm a clear X-shape in the [Fe/H] and density distributions at large Galactic heights. Conclusions. The orbital structure obtained for the APOGEE stars reveals that the Milky Way hosts an inner ring-like structure between the planar bar and corotation. This structure is on average metal rich, intermediately aged, and enhances the horizontal metallicity gradient along the bar’s major axis.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Study of beyond nearest-neighbor environment and intermediate-range order in a sodium aluminosilicate geopolymer using Reverse Monte Carlo modeling

A large scale three-dimensional structural model of a geopolymer with an approximate composition of NaAlSi 2 O 6 .5.5H 2 O obtained by Reverse Monte Carlo (RMC) modeling based on experimental high-energy x-ray diffraction is presented for the first time in order to obtain information regarding beyond nearest-neighbor environment and intermediate-range order (IRO). RMC model exhibits a three-dimensional network consisting of randomly cross-linked AlO 4 and SiO 4 tetrahedral units with uniformly distributed Na atoms and H 2 O molecules. The bond angle distributions, i.e. T-O-T, O-T-O and Na-O-Na angles, are somewhat distorted with lower values compared to analogous crystal systems. The origin of the first peak in the structure factor indicating IRO is investigated using the partial structure factors; Na-Na, Si-Na, Al-Si, O-H, and H-H atom pairs are found to be the main contributors. Ring size distribution analysis demonstrates that the structure mainly involves 6-, 7- and 8-membered rings. Finally, the coherence length of these IRO characteristics is ~10.3 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Viscoelasticity-induced structure anisotropy in amorphous materials

Viscoelasticity-induced structural change in Zr 55 Cu 30 Ni 5 Al 10 metallic glass (Zr-MG) and amorphous selenium (a-Se) is investigated using synchrotron X-ray diffraction. By analyzing the two-dimensional diffraction pattern, two types of structural anisotropy with the feature of the residual elastic strain or heterogeneous intensity of diffraction rings are revealed. The origin of the structural anisotropy is attributed to the topological rearrangement in the Zr-MG and conformation rearrangement in the a-Se. In conclusion, our findings bring a structural identity to the phenomenological structureless deformation defect widely used in different amorphous materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The effect of thread-like monomer structure on the synthesis of poly[ n ]catenanes from metallosupramolecular polymers

The main-chain poly[n]catenane consists of a series of interlocked rings that resemble a macroscopic chain-link structure. Recently, the synthesis of such intriguing polymers was reported via a metallosupramolecular polymer (MSP) template that consists of alternating units of macrocyclic and linear thread-like monomers. Ring closure of the thread components has been shown to yield a mixture of cyclic, linear, and branched poly[n]catenanes. Reported herein are studies aimed at accessing new poly[n]catenanes via this approach and exploring the effect the thread-like monomer structure has on the poly[n]catenane synthesis. Specifically, the effect of the size of the aromatic linker and alkenyl chains of the thread-like monomer is investigated. Three new poly[n]catenanes (with different ring sizes) were prepared using the MSP approach and the results show that tailoring the structure of the thread-like monomer can allow the selective synthesis of branched poly[n]catenanes.

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

Imidazole-graphyne: a new 2D carbon nitride with a direct bandgap and strong IR refraction

Six-membered rings are common building blocks of many carbon structures. Recent studies have shown that penta-graphene composed of five-membered carbon rings have properties very different from that of graphene. This has motivated the search for new carbon structures. Among this is cp-graphyne, composed of carbon pentagons and bridged by acetylenic linkers. However, the bandgap of cp-graphyne, like that of graphene, is zero, making it unsuitable for applications in electronics. Herein, we show that a new two-dimensional (2D) carbon nitride structure formed by assembling the five-membered imidazole molecules with acetylenic linker can overcome this limitation. Named ID-GY, this new material not only has a direct band gap of 1.10 eV, but it is dynamically and mechanically stable and can withstand temperatures up to 1200 K. In addition, due to its porous and anisotropic geometry, the Young's modulus of ID-GY along the diagonal direction is lower than that of most 2D materials reported previously. Equally important, ID-GY exhibits strong refraction near infrared (IR) and has potential for applications in nanoelectronics and optical devices. These results, based on density functional theory, can stimulate experimental studies.

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

Evolutionary inverse design of defects at graphene 2D lateral interfaces

Grain boundaries (GBs) in two-dimensional (2D) materials often have a profound impact on various material properties from mechanical to optical to electronic, yet predicting all possible GB formations is a challenge. Here, we introduce a workflow based on an evolutionary algorithm for exploring possible GBs formed at a lateral 2D interface. In a departure from conventional genetic algorithm based structure optimization methods, we perform genetic operations in the near interface region that allow us to be computationally efficient. We benchmark our method using graphene, which is a well-studied 2D material with a wide range of point defects. An empirical potential was used as the surrogate of the evolutionary search. More than 11.5 × 106 structures in total were evaluated for 128 GB orientations, and for each orientation, the ten best structures are recorded. A subset of low energy GBs predicted by empirical potential based search was relaxed by first-principles calculations and used to validate the energetic rank order. With the validated formation energy, we rank-ordered the best 128 GB structures and performed a detailed statistical analysis of primitive rings to find the correlation between the ring distribution and the formation energy. We found that for low energy GBs (below 0.5eV/Å), Stone–Wales defects will dominate, while structures with a higher energy (0.5–1.1eV/Å) show an increasing population of heptagons and nine-membered rings to form seven-nine defect pairs. For structures with energy higher than 1.1eV/Å, the percentage of octagons and nine-membered rings increases, which indicates that these two types of rings are not energetically favorable. Our proposed methodology is broadly applicable to explore defective low dimensional materials and represents a powerful tool that enables a systematic search of GBs of lateral interfaces for 2D materials.

Zhang, Jianan↗
DOE OSTI2025

Machine learning-assisted profiling of a kinked ladder polymer structure using scattering

Ladder polymers consisting of fused rings in the backbone have very limited conformational freedom, which results in very different properties from traditional linear polymers. However, accurately determining their size and chain conformations from solution scattering remains a challenge. Their chain conformations of kinked ladder polymers are largely governed by the structures and relative orientations or configurations of the repeat units, unlike conventional polymer chains whose bending angles between repeat units follow a unimodal Gaussian distribution. Meanwhile, traditional scattering models for polymer chains do not account for these unique structural features. This work introduces a novel approach that integrates machine learning with Monte Carlo simulations to construct a model that can describe the geometry of a type of kinked CANAL ladder polymers. We first develop a Monte Carlo simulation model for sampling the configuration space of CANAL ladder polymers, where each repeat unit is modeled as a biaxial segment. Then, we establish a machine learning-assisted scattering analysis framework based on Gaussian Process Regression. Finally, we conduct small-angle neutron scattering experiments on a CANAL ladder polymer solution to apply our approach. Our method uncovers structural features of such ladder polymers that conventional methods fail to capture.

Ding, Lijie [Oak Ridge National Laboratory (ORNL),↗
DOE OSTI2022

Modeling and implementation of vertical excursion FFA in the Zgoubi ray-tracing code

Vertical Fixed Field Accelerators (vFFAs) feature complex and highly non-linear magnetic fields, which require simulation codes allowing step-wise particle tracking. Methods to model the 3D magnetic field of scaling vFFAs have been developed in the ray-tracing code Zgoubi. The field modeling and particle tracking methods include the field non-linearities, the fringe fields, and the field superposition of neighboring magnets. The procedure implements the vFFA analytical field expressions, allowing design studies and parameter optimizations using the Zgoubi built-in fit method. The vFFA procedure has been applied to a ten-fold symmetry ring with a triplet focusing structure designed to accelerate protons from 3 MeV to 12 MeV and studied under the ISIS-II proton driver prototype project. Results from particle tracking in externally generated 3D semi-analytical field maps and the developed vFFA analytical model are shown to be in excellent agreement.

43 PARTICLE ACCELERATORS↗
DOE OSTI2020

Formation of phenanthrenyl radicals via the reaction of acenaphthyl with acetylene

Ab initio G3(MP2,CC)/B3LYP/6–31G** calculations of the potential energy surface for the reaction of 3-acenaphthyl radical with acetylene were combined with Rice-Ramsperger-Kassel-Marcus Master Equation calculations of the temperature- and pressure-dependent reaction rate constants and product branching ratios with the goal to examine the transformation of an edge five-membered ring into a six-membered one. The reaction mechanism has been shown to contain two stages: (1) the formation of 3-ethynylacenaphthylene + H in the 3-acenaphthyl + C 2 H 2 reaction via acetylene addition to the radical site and an H loss, (2) the formation of the 1-phenanthrenyl radical in the 3-ethynylacenaphthylene + H reaction via H addition to the five-membered ring followed by the ring flip. The results of kinetic modeling show this pathway being faster than the pathway proposed earlier featuring the CCH chemisorption on the six-membered ring without involvement of the five-membered ring. A kinetic test demonstrated the dominance of the former pathway for the formation of pyrene from naphthalene. Here, it is expected that the new mechanism plays a major role in the transformation of five-membered rings on edges of PAH structures.

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

Modifying the Optical Emission of Vanadyl Phthalocyanine via Molecular Self-Assembly on van der Waals Materials

Vanadyl phthalocyanine (VOPc) is a promising organic molecule for applications in quantum information because of its thermal stability, efficient processing, and potential as a spin qubit. The deposition of VOPc in different molecular orientations allows the properties to be customized for integration into various devices. However, such customization has yet to be fully leveraged to alter its intrinsic properties, particularly optical emission. Normally, VOPc films on dielectric substrates emit a broad photoluminescence peak in the near-infrared range, attributed to transitions in the Pc ring from its π orbital structure. Here, in this work, we demonstrate that the dominant optical transition of VOPc can be shifted by ∼250 meV through the controlled deposition of thin films on van der Waals material substrates. The weak interactions with van der Waals materials allow the molecules to uniquely self-assemble, resulting in modified optical behavior modulated by the molecular phase and thickness. This work connects the self-assembling properties of molecules to their altered electronic structures and the resulting optical emission.

anions↗
DOE OSTI2020

Role of Intact Hydrogen-Bond Networks in Multiproton-Coupled Electron Transfer

The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole–phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-protoncoupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (~1000 mV s –1 ) a chemically reversible process is observed with an E 1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s –1 ) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. Furthermore, this work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗