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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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Few‐Unit‐Cell MFI Zeolite Synthesized using a Simple Di‐quaternary Ammonium Structure‐Directing Agent

Abstract Synthesis of a pentasil‐type zeolite with ultra‐small few‐unit‐cell crystalline domains, which we call FDP (few‐unit‐cell crystalline domain pentasil), is reported. FDP is made using bis‐1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di‐quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five‐carbon nitrogen‐connecting chain, in place of the six‐carbon connecting chain SDAs that are known to fit well within the MFI pores. X‐ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10 nm crystalline domains organized in hierarchical micro‐/meso‐porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5 μm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol‐to‐hydrocarbon and glucose isomerization catalysts, respectively.

Lu, Peng↗
DOE OSTI2022

The Interaction of K and O 2 on Au(111): Multiple Growth Modes of Potassium Oxide and Their Catalytic Activity for CO Oxidation

Abstract In industrial catalysis, alkali cations are frequently used to promote activity or selectivity. Scanning tunneling microscopy, ambient‐pressure X‐ray photoelectron spectroscopy, and density‐functional calculations were used to study the structure and reactivity of potassium oxides in contact with the Au(111) surface. Three different types of oxides (K 2 O 2 , K 2 O and KO y with y <0.5) were observed on top of the gold substrate at 300–525 K. Initially, small aggregates of K 2 O 2 /K 2 O (1–2 nm in size) were seen at the elbows of the herringbone structure. After increasing the K coverage (>0.15 ML), large islands of the oxide (20–40 nm in size) appeared. These islands contained a mixture of K 2 O and KO y ( y <0.5). A key correlation was found involving the structure, oxidation state, and chemical activity of the alkali oxide. The small aggregates of potassium oxide had a very high catalytic activity for the oxidation of CO, being much more than plain promoters.

Shi, Rui↗
DOE OSTI2022

Two‐Dimensional Excitonic Networks Directed by DNA Templates as an Efficient Model Light‐Harvesting and Energy Transfer System

Abstract Photosynthetic organisms organize discrete light‐harvesting complexes into large‐scale networks to facilitate efficient light collection and utilization. Inspired by nature, herein, synthetic DNA templates were used to direct the formation of dye aggregates with a cyanine dye, K21, into discrete branched photonic complexes, and two‐dimensional (2D) excitonic networks. The DNA templates ranged from four‐arm DNA tiles, ≈10 nm in each arm, to 2D wireframe DNA origami nanostructures with different geometries and varying dimensions up to 100×100 nm. These DNA‐templated dye aggregates presented strongly coupled spectral features and delocalized exciton characteristics, enabling efficient photon collection and energy transfer. Compared to the discrete branched photonic systems templated on individual DNA tiles, the interconnected excitonic networks showed approximately a 2‐fold increase in energy transfer efficiency. This bottom‐up assembly strategy paves the way to create 2D excitonic systems with complex geometries and engineered energy pathways.

Zhou, Xu↗
DOE OSTI2021

Few‐Unit‐Cell MFI Zeolite Synthesized using a Simple Di‐quaternary Ammonium Structure‐Directing Agent

Abstract Synthesis of a pentasil‐type zeolite with ultra‐small few‐unit‐cell crystalline domains, which we call FDP (few‐unit‐cell crystalline domain pentasil), is reported. FDP is made using bis‐1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di‐quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five‐carbon nitrogen‐connecting chain, in place of the six‐carbon connecting chain SDAs that are known to fit well within the MFI pores. X‐ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10 nm crystalline domains organized in hierarchical micro‐/meso‐porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5 μm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol‐to‐hydrocarbon and glucose isomerization catalysts, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Interaction of K and O 2 on Au(111): Multiple Growth Modes of Potassium Oxide and Their Catalytic Activity for CO Oxidation

Abstract In industrial catalysis, alkali cations are frequently used to promote activity or selectivity. Scanning tunneling microscopy, ambient‐pressure X‐ray photoelectron spectroscopy, and density‐functional calculations were used to study the structure and reactivity of potassium oxides in contact with the Au(111) surface. Three different types of oxides (K 2 O 2 , K 2 O and KO y with y <0.5) were observed on top of the gold substrate at 300–525 K. Initially, small aggregates of K 2 O 2 /K 2 O (1–2 nm in size) were seen at the elbows of the herringbone structure. After increasing the K coverage (>0.15 ML), large islands of the oxide (20–40 nm in size) appeared. These islands contained a mixture of K 2 O and KO y ( y <0.5). A key correlation was found involving the structure, oxidation state, and chemical activity of the alkali oxide. The small aggregates of potassium oxide had a very high catalytic activity for the oxidation of CO, being much more than plain promoters.

Shi, Rui↗
DOE OSTI2022

Two–Dimensional Excitonic Networks Directed by DNA Templates as an Efficient Model Light–Harvesting and Energy Transfer System

Photosynthetic organisms organize discrete light-harvesting complexes into large-scale networks to facilitate efficient light collection and utilization. Inspired by nature, herein, synthetic DNA templates were used to direct the formation of dye aggregates with a cyanine dye, K21, into discrete branched photonic complexes, and two-dimensional (2D) excitonic networks. The DNA templates ranged from four-arm DNA tiles, ≈10 nm in each arm, to 2D wireframe DNA origami nanostructures with different geometries and varying dimensions up to 100×100 nm. These DNA-templated dye aggregates presented strongly coupled spectral features and delocalized exciton characteristics, enabling efficient photon collection and energy transfer. Compared to the discrete branched photonic systems templated on individual DNA tiles, the interconnected excitonic networks showed approximately a 2-fold increase in energy transfer efficiency. Lastly, this bottom-up assembly strategy paves the way to create 2D excitonic systems with complex geometries and engineered energy pathways.

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

Nonfullerene Acceptor Featuring Unique Self‐Regulation Effect for Organic Solar Cells with 19 % Efficiency

Abstract The blend nanomorphology of electron‐donor (D) and ‐acceptor (A) materials is of vital importance to achieving highly efficient organic solar cells. Exogenous additives especially aromatic additives are always needed to further optimize the nanomorphology of blend films, which is hardly compatible with industrial manufacture. Herein, we proposed a unique approach to meticulously modulate the aggregation behavior of NFAs in both crystal and thin film nanomorphology via self‐regulation effect. Nonfullerene acceptor Z9 was designed and synthesized by tethering phenyl groups on the inner side chains of the Y6 backbone. Compared with Y6, the tethered phenyl groups participated in the molecular aggregation via the π–π stacking of phenyl‐phenyl and phenyl‐2‐(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (IC‐2F) groups, which induced 3D charge transport with phenyl‐mediated super‐exchange electron coupling. Moreover, ordered molecular packing with suitable phase separation was observed in Z9‐based blend films. High power conversion efficiencies (PCEs) of 19.0 % (certified PCE of 18.6 %) for Z9‐based devices were achieved without additives, indicating the great potential of the self‐regulation strategy in NFA design.

Chemistry↗
DOE OSTI2024

Impact of Iron Species Dispersion on Fe/ZSM–5 Catalyst Performance for Methane Dehydroaromatization (MDA)

Methane dehydroaromatization (MDA) is one of the most promising technologies for directly transforming methane into aromatics. Unlike the extensively investigated Mo/ZSM-5 catalysts, the structure and, consequently, the catalytic activity of Fe/ZSM-5 are markedly influenced by the method of preparation, as shown here. In this study, we prepared 2 % and 4 % Fe/ZSM-5 catalysts via wet impregnation (WI) and incipient wetness impregnation (IWI). Characterizations (XRD, STEM, UV-Vis, NH 3 -TPD and H 2 -TPR) reveal that 2 %Fe-WI mainly possesses isolated or low-polymerized Fe species within zeolite channels, leading to a rapid activation and a higher benzene yield due to the faster reduction to iron suboxides under MDA conditions. In contrast, 2 %Fe-IWI contains bulk iron oxide aggregates, resulting in a slower activation as these aggregates transform into iron carbide through successive reduction and carbonization. Here, a deactivation kinetic study applied to the 2 % catalysts further demonstrates the quantitative relation between Fe site isolation and catalytic activity. Although both 4 % catalysts inevitably form sizable iron oxide clusters and particles due to the high Fe/Al ratio, similar trends are noted, with the WI catalysts exhibiting a shorter induction/activation period and a higher yield of benzene, paralleling observations made with 2 % catalysts.

03 NATURAL GAS↗
DOE OSTI2022

Determination of the Structures of Lignin Subunits and Nanoparticles in Solution by Small‐Angle Neutron Scattering: Towards Improving Lignin Valorization

Abstract Lignin nanoparticles (LNPs) are usually produced from lignin solution through supersaturation. The structure of the lignin in solution is still poorly understood due to structural variability of isolated lignins. Here, lignins were extracted from different plants to establish a general pattern of their structure in several lignin solvents. Lignin molecules (lignin subunits) and larger aggregates were observed in dimethyl sulfoxide (DMSO), ethylene glycol (EG) and 0.1 N NaOD solutions by small‐angle neutron scattering (SANS). It was proposed that the aggregates were composed of lignin subunits with a higher molecular weight and a higher ratio of the aliphatic to phenolic hydroxyl groups. The size, shape, and compactness are important factors that affect the uses of the LNPs, which were obtained from the SANS data for the first time. A discrepancy in the radius between SANS and DLS was discovered, pointing to a large hydration shell around the LNPs in aqueous solutions. The cytotoxicity of the corncob lignin, kraft lignin, and their LNPs were measured and compared.

Zhang, Xin↗
DOE OSTI2022

In‐operando crystallization study of zinc nitrate hexahydrate using zinc oxide nucleators

Abstract Supercooling (∆T Sup ) is one of the crucial problems in utilizing a phase change material (PCM), which has been attempted to overcome using nucleators possessing small lattice disregistry without comprehensive understanding of the nucleation phenomenon. Here, this work studies the interactions between nucleators and PCM via in‐operando direct visualization for the first time, to the best of our knowledge, to better understand the crystallization process during freezing of a PCM using zinc nitrate hexahydrate (ZNH) and a zinc oxide (ZnO) nucleator. According to our in‐operando study, freezing was randomly initiated by only a fraction of the nucleator particles during each thermal cycling. However, previously unresponsive nucleators also suddenly crystalized PCM when the propagating crystal encountered them, improving the crystal initiation and thereby ∆T Sup . Consequently, for equal wt% of ZnO, better nucleation behavior was obtained using uniformly distributed small nucleator particles throughout the PCM, as compared to either large or poorly distributed aggregated nucleators. DSC results using ZnO‐needle as nucleator confirmed a 38% and 33.3% lower ∆T Sup upon employing 5 wt% small (individual) particles (~4 μm on average), as compared to using equal wt% of small (aggregated) particle clusters (~200 μm) and large particles (~46 μm), respectively. Crystallization of ZNH caused additional hair‐like ZnO growth preferentially decorated along lateral faces of the original nucleator particles. The in‐operando studies are valuable tools to correlate inherent crystallization phenomena to the practical thermal energy storage properties of the system.

Chakraborty, Anirban↗
DOE OSTI2020

Lipids status and copper in a single astrocyte of the rat model for amyotrophic lateral sclerosis: Correlative synchrotron-based X-ray and infrared imaging

Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease, causing death of motor neurons controlling voluntary muscles. The pathological mechanisms of the disease are only partially understood. The hSOD1-G93A ALS rat model is characterized by an overexpression of human mutated SOD1, causing increased vulnerability by forming intracellular protein aggregates, inducing excitotoxicity, affecting oxidative balance and disturbing axonal transport. In this study we followed the bio-macromolecular organic composition and compartmentalization together with trace metal distribution in situ in single astrocytes from the ALS rat model and compared them to the control astrocytes from nontransgenic littermates by simultaneous use of two synchrotron radiation-based methods: Fourier transform infrared microspectroscopy (SRFTIR) and hard X-ray fluorescence microscopy (XRF). Here we show that ALS cells contained more Cu, which colocalized with total lipids, increased carbonyl groups and oxidized lipids, thus implying direct involvement of Cu in oxidative stress of lipidic components without direct connection to protein aggregation in situ.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Ionic Liquid Facilitated Solvent‐Phase Polymerization of Ultrasmooth Coatings of Polycatecholamines

Mussel-inspired polycatecholamine coatings and films have proven to be versatile materials for surface modification. However, the progress of chemically modified coatings with tailored properties has been slow due to the lack of definitive evidence of their polymeric structure. Polycatecholamines form aggregates during polymerization, and their formation mechanism has been a subject of debate owing to their insolubility in traditional molecular solvents. Exploiting the capability of ionic liquids (ILs) to exhibit strong electrostatic interactions, herein, the first solution-phase polymerization approach is reported to achieve polymerization of four catecholamines – dopamine (DA), norepinephrine (NE), L-3,4-dihydroxyphenylalanine (L-DOPA), and adrenaline (AD). Kinetic control over the polymerization process in the solution phase enabled it to follow the process with 1 H NMR spectroscopy, revealing the formation of structural features of resulting complex heterogeneous and soluble polymers. The polymers are both covalent and associative in nature. Solution phase polymerization prevented the formation of large aggregates in the solution, thus facilitating the formation of coatings that are ultra-smooth and have root mean square roughness of the order of sub-nm to nm scale.

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

Preferred Void Orientation in Uniaxially Pressed PBX 9502

Ultra- and small-angle neutron scattering techniques were used to study the morphology of voids in directions parallel and perpendicular to the compaction plane of a uniaxially pressed cylinder of PBX 9502. Two-dimensional scattering patterns from samples cut parallel to the compaction plane had circular equal-intensity contours, implying that along this view the voids are circular or randomly oriented. Identical measurements of samples cut perpendicular to the compaction plane produced elliptical equal-intensity contours, indicating preferred orientation of voids. Analysis of the two dimensional scattering patterns confirmed that the voids are non-spherical with an average aspect ratio of 1.20, flattened so that the larger dimensions of the voids lie within the compaction plane. Model analysis of the combined ultra- and small-angle neutron scattering curves revealed that the PBX 9502 porosity is interconnected, in the form of aggregates comprised of non-spherical, primary voids. The volume dimension was found to be the same in both directions, indicating that the aggregate is randomly oriented throughout the sample, and that it is the primary voids that are preferentially oriented. Furthermore, void interfaces with the surrounding matrix were found to be rough or polydisperse, with a common roughness dimension or polydispersity in all directions.

42 ENGINEERING↗
DOE OSTI2023

Structural insights into the unique recognition module between α-synuclein peptide and nanobody

Nanobodies are single-domain fragments of antibodies with comparable specificity and affinity to antibodies. They are emerging as versatile tools in biology due to their relatively small size. Here, we report the crystal structure of a specific nanobody Nbα-syn01, bound to a 14 amino acid long peptide of α-synuclein (αSyn), a 140-residue protein whose aggregation is associated with Parkinson's disease. The complex structure exhibits a unique binding pattern where the αSyn peptide replaces the N-terminal region of nanobody. Recognition is mediated principally by extended main chain interaction of the αSyn peptide and specificity of the interaction lies in the central 48–52 region of αSyn peptide. Structure-guided truncation of Nbα-syn01 shows tighter binding to αSyn peptide and improved inhibition of α-synuclein aggregation. The structure of the truncated complex was subsequently determined and was indistinguishable to full length complex as the full-length form had no visible electron density for the N-terminal end. These findings reveal the molecular basis for a previously unobserved binding mode for nanobody recognition of α-synuclein, providing an explanation for the enhanced binding, and potential for an alternate framework for structure-based protein engineering of nanobodies to develop better diagnostic and therapeutic tools.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Long‐term changes in soil carbon and nitrogen fractions in switchgrass, native grasses, and no‐till corn bioenergy production systems

Cellulosic bioenergy is a primary land-based climate mitigation strategy, with soil carbon (C) storage and nitrogen (N) conservation as important mitigation elements. Here, we present 13 years of soil C and N change under three cellulosic cropping systems: monoculture switchgrass (Panicum virgatum L.), a five native grasses polyculture, and no-till corn (Zea mays L.). Soil C and N fractions were measured four times over 12 years. Bulk soil C in the 0–25 cm depth at the end of the study period ranged from 28.4 (± 1.4 se) Mg C ha −1 in no-till corn, to 30.8 (± 1.4) Mg C ha −1 in switchgrass, and to 34.8 (± 1.4) Mg C ha −1 in native grasses. Mineral-associated organic matter (MAOM) ranged from 60% to 90% and particulate organic matter (POM) from 10% to 40% of total soil C. Over 12 years, total C as well as both C fractions persisted under no-till corn and switchgrass and increased under native grasses. In contrast, POM N stocks decreased 33% to 45% across systems, whereas MAOM N decreased only in no-till corn and by less than 13%. Declining POM N stocks likely reflect pre-establishment land use, which included alfalfa and manure in earlier rotations. Root production and large soil aggregate formation explained 69% (p < 0.001) and 36% (p = 0.024) of total soil C change, respectively, and 60% (p = 0.020) and 41% (p = 0.023) of soil N change, demonstrating the importance of belowground productivity and soil aggregates for producing and protecting soil C and conserving soil N. Differences between switchgrass and native grasses also indicate a dependence on plant diversity. Soil C and N benefits of bioenergy crops depend strongly on root productivity and pre-establishment land use.

09 BIOMASS FUELS↗
DOE OSTI2020

Quantized Grain Boundary States Promote Nanoparticle Alignment During Imperfect Oriented Attachment

Oriented attachment (OA) has become a well-recognized mechanism for the growth of metal, ceramic, and biomineral crystals. While many computational and experimental studies of OA have shown that particles can attach with some misorientation then rotate to remove adjoining grain boundaries, the underlying atomistic pathways for this “Imperfect OA” process remain the subject of debate. In this paper, molecular dynamics and in situ TEM were used to probe the crystallographic evolution of up to 30 gold and copper nanoparticles during aggregation. It was found that Imperfect OA occurs because (1) grain boundaries become quantized when their size is comparable to the separation between constituent dislocations and (2) kinetic barriers associated with the glide of grain boundary dislocations are small. In support of these findings, TEM experiments show the formation of a single crystal aggregate after annealing 9 initially misoriented, agglomerated particles with evidence of dislocation slip and twin formation during particle/grain alignment. These observations motivate future work on assembled nanocrystals with tailored defects and call for a revision of Read-Shockley models for grain boundary energies in nanocrystalline materials.

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

Pressure–Modulated Luminescence Enhancement and Quenching in a Hydrogen–Bonded Organic Framework

Light emission in the solid state is central for illumination, sensing, and imaging applications. Unlike luminescence in dilute solutions, where the excited states are unimolecular in nature, intermolecular interaction plays a significant role in the quantum yield of solid-state luminophores, manifested as competing aggregation-caused quenching (ACQ) and aggregation-induced enhancement (AIE). Both effects are extensively studied in various systems; however, it remains unclear how their competition depends on molecular conformation and intermolecular stacking. Here the direct observation of pressure-modulated AIE-ACQ competition in a crystalline hydrogen-bonded organic framework (HOF) is reported. Using in situ spectroscopies and computational modeling, the intramolecular vibration and intermolecular π–π stacking directly responsible for the non-radiative decay of the excited state are identified. The extent of these two contributions is modulated by hydrostatic pressure and guest molecules in the HOF pores. Furthermore, this work demonstrates a physically neat model system to understand and control solid-state luminescence, and a potential material platform for piezoluminescent sensing.

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

De Nive Quinquangula: Pentagonal Snowflake Metal Nanocrystals as an Example of Emergence Phenomenon in Nanotechnology Complex Systems

The formation of snowflakes (SFL) is one of the most captivating phenomena in nature. The fabrication of multimetallic gold (Au) nanoparticles containing copper (Cu) and iron (Fe) is reported, which adopt snowflake-like morphology after nanoparticle aggregation. The synthesis of these snowflake-like Au microcrystals occurs mainly by kinetic control. In this process, a surfactant-assisted salt reduction method is employed on a heated substrate. Here, the metal salts react within seconds to form nanoparticles. This process results in a hierarchical structure with pseudo-pentagonal symmetry and chiroptical activity. We discuss how large superstructures emerge from nanoparticle aggregation, resembling natural snowflakes. However, unlike ice snowflakes, which exhibit hexagonal symmetry, the Au snowflakes display pentagonal symmetry. It is proposed that the formation of these snowflake-like microcrystals is the result of the complexity involved in the crystal growth process and represents an example of the phenomenon of emergence, which has become very significant in several fields of modern science, including physics, biology, chemistry, economics, philosophy, and poetry. The term emergent is used to evoke the collective behavior of a large number of microscopic constituents that is qualitatively different than the behaviors of the individual constituents.

36 MATERIALS SCIENCE↗