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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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Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms
Not provided.
Unprecedented peroxidase-mimicking activity of single-atom nanozyme with atomically dispersed Fe–Nx moieties hosted by MOF derived porous carbon
Due to robustness, easy large-scale preparation and low cost, nanomaterials with enzyme-like characteristics (defined as ‘nanozymes’) are attracting increasing interest for various applications. However, most of currently developed nanozymes show much lower activity in comparison with natural enzymes, and the deficiency greatly hinders their use in sensing and biomedicine. Single-atom catalysts (SACs) offer the unique feature of maximum atomic utilization, providing a potential pathway to improve the catalytic activity of nanozymes. Herein, we propose a Fe-N-C single-atom nanozyme (SAN) that exhibits unprecedented peroxidase-mimicking activity. The SAN consists of atomically dispersed Fe-Nx moieties hosted by metal–organic frameworks (MOF) derived porous carbon. Thanks to the 100% single-atom active Fe dispersion and the large surface area of the porous support, the Fe-N-C SAN provided a specific activity of 57.76 U mg-1, which was almost at the same level as natural horseradish peroxidase (HRP). Attractively, the SAN presented much better storage stability and robustness against harsh environments. As a proof-of-concept application, highly sensitive biosensing of butyrylcholinesterase (BChE) activity using the Fe-N-C SAN as a substitute for natural HRP was further verified.
Fast Atomic-Scale Elemental Mapping of Crystalline Materials by STEM Energy-Dispersive X-Ray Spectroscopy Achieved with Thin Specimens [Fast Atomic-Scale Chemical Imaging of Crystalline Materials by STEM Energy-Dispersive X-ray Spectroscopy Achieved with Thin Specimens].
Abstract Elemental mapping at the atomic-scale by scanning transmission electron microscopy (STEM) using energy-dispersive X-ray spectroscopy (EDS) provides a powerful real-space approach to chemical characterization of crystal structures. However, applications of this powerful technique have been limited by inefficient X-ray emission and collection, which require long acquisition times. Recently, using a lattice-vector translation method, we have shown that rapid atomic-scale elemental mapping using STEM-EDS can be achieved. This method provides atomic-scale elemental maps averaged over crystal areas of ~few 10 nm 2 with the acquisition time of ~2 s or less. Here we report the details of this method, and, in particular, investigate the experimental conditions necessary for achieving it. It shows, that in addition to usual conditions required for atomic-scale imaging, a thin specimen is essential for the technique to be successful. Phenomenological modeling shows that the localization of X-ray signals to atomic columns is a key reason. The effect of specimen thickness on the signal delocalization is studied by multislice image simulations. The results show that the X-ray localization can be achieved by choosing a thin specimen, and the thickness of less than about 22 nm is preferred for SrTiO 3 in [001] projection for 200 keV electrons.
Combined Experimental and Computational Investigation of the Elementary Reaction of Ground State Atomic Carbon (C; 3 P j ) with Pyridine (C 5 H 5 N; X 1 A 1 ) via Ring Expansion and Ring Degradation Pathways
In t his work, we explored the elementary reaction of atomic carbon (C; 3 P j ) with pyridine (C 5 H 5 N; X 1 A 1 ) at a collision energy of 34 ± 4 kJ mol-1 utilizing the crossed molecular beams technique. Forwardconvolution fitting of the data was combined with high-level electronic structure calculations and statistical (RRKM) calculations on the triplet C 6 H 5 N potential energy surface (PES). These investigations reveal that the reaction dynamics are indirect and dominated by large range reactive impact parameters leading via barrier-less addition to the nitrogen atom and to two chemically non-equivalent ‘aromatic’ carbon-carbon bonds forming three distinct collision complexes. At least two reaction pathways through atomic hydrogen loss were identified on the triplet surface. These channels involve multiple isomerization steps of the initial collision complexes via ring-opening and ring expansion forming an acyclic 1-ethynyl-3-isocyanoallyl radical (P1; 2 A”) and a hitherto unreported seven-membered 1-aza-2-dehydrocyclohepta-2,4,6-trien-4-yl radical isomer (P3; 2 A), respectively. For RRKM calculations at zero collision energy, representing conditions in cold molecular clouds, the ring expansion product P3 is formed nearly exclusively for the atomic hydrogen loss channel. Based on the computations, the molecular fragmentation channel eliminating acetylene (C 2 H 2 ) plus 3-cyano-2-propen-1-ylidene (P6; 3 A”) plays also an important role the reaction of atomic carbon with pyridine proposing a probable destruction pathway of interstellar pyridine. Lastly, these results are also discussed in light of the isoelectronic carbon – benzene (C 6 H 6 ; X 1 A 1 ) system with important implications to the rapid degradation of nitrogen-bearing polycyclic aromatic hydrocarbons (NPAHs) in the interstellar medium compared to mass growth processes of PAH counterparts through ring expansion.
H Atom Production and Reaction in the Gamma Radiolysis of Thermally Modified Boehmite
The correlation between the formation of H atoms and H2 was observed in the radiolysis of thermally modified boehmite (?-AlOOH). Boehmite was pretreated by heating to 300, 400, and 550°C, loaded with adsorbed water, and irradiated with gamma rays. Long-lived H atoms trapped in the interstitial matrix was observed by electron paramagnetic resonance techniques and the amount of gaseous H2 by gas chromatography. Heating the boehmite to 400°C before radiolysis results in the collapse of the matrix with loss of trapped H atoms and a substantial increase in the production of H2. Samples without added water post-heating showed no production of H2 suggesting that it is formed by the diffusion of H atoms to the surface followed by an abstraction reaction with water. Boehmite heated to 550°C has completely converted to alumina and the radiolytic responses of each are similar. Post-irradiation heating of boehmite to 300°C results in a doubling of the H2 yield at pretreated temperatures below 300°C due to the release of trapped H atoms.
Atomic-scale Mechanisms of Enhanced Electrochemical Properties of Mo-doped Co-free Layered Oxide Cathodes for Lithium-Ion Batteries
Cobalt-free layered oxides with high specific capacity and low cost have emerged as promising candidates for next-generation cathodes for lithium-ion batteries. However, implementation of these materials has been hindered by their low rate capability, structural instability, and rapid capacity decay during cycling. Recent studies have shown that introducing cation dopants into layered oxides can strongly improve their electrochemical properties, but the underlying mechanisms remain elusive due to a lack of information at the atomic scale. In this work, we use a combination of atomic-resolution scanning transmission electron microscopy and first principle calculations to reveal the microscopic origin of enhanced electrochemical properties in LiNi0.5Mn0.5O2 doped with ~1 at % Mo. These results indicate that the Mo dopant hinders Li+/Ni2+ cation mixing and suppresses detrimental phase transformations near the particle surface and at grain boundaries, which enhances the cathode’s reversible capacity and cycling stability. Overall, This work provides important insights on how cation doping affects the structure and electrochemical properties of layered oxide cathodes.
Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit
Abstract not provided
Atomic-scale 3D imaging of individual dopant atoms in an oxide semiconductor
The physical properties of semiconductors are controlled by chemical doping. In oxide semiconductors, small variations in the density of dopant atoms can completely change the local electric and magnetic responses caused by their strongly correlated electrons. In lightly doped systems, however, such variations are difficult to determine as quantitative 3D imaging of individual dopant atoms is a major challenge. We apply atom probe tomography to resolve the atomic sites that donors occupy in the small band gap semiconductor Er(Mn,Ti)O 3 with a nominal Ti concentration of 0.04 at. %, map their 3D lattice positions, and quantify spatial variations. Our work enables atomic-level 3D studies of structure-property relations in lightly doped complex oxides, which is crucial to understand and control emergent dopant-driven quantum phenomena.
Mending cracks atom-by-atom in rutile TiO2 with electron beam radiolysis
Abstract Rich electron-matter interactions fundamentally enable electron probe studies of materials such as scanning transmission electron microscopy (STEM). Inelastic interactions often result in structural modifications of the material, ultimately limiting the quality of electron probe measurements. However, atomistic mechanisms of inelastic-scattering-driven transformations are difficult to characterize. Here, we report direct visualization of radiolysis-driven restructuring of rutile TiO 2 under electron beam irradiation. Using annular dark field imaging and electron energy-loss spectroscopy signals, STEM probes revealed the progressive filling of atomically sharp nanometer-wide cracks with striking atomic resolution detail. STEM probes of varying beam energy and precisely controlled electron dose were found to constructively restructure rutile TiO 2 according to a quantified radiolytic mechanism. Based on direct experimental observation, a “two-step rolling” model of mobile octahedral building blocks enabling radiolysis-driven atomic migration is introduced. Such controlled electron beam-induced radiolytic restructuring can be used to engineer novel nanostructures atom-by-atom.
Atomic interface effect of a single atom copper catalyst for enhanced oxygen reduction reactions
The regulation of catalytic activity in the oxygen reduction reaction (ORR) is significant to the development of metal–air batteries and other oxygen involving energy conversion devices. Herein, we propose an atomic interface strategy to construct a single atom copper catalyst (denoted as Cu-SA/SNC) which exhibits enhanced ORR activity with a half-wave potential of 0.893 V vs. RHE in alkaline media. Moreover, synchrotron-radiation-based X-ray absorption fine structure (XAFS) investigations together with density functional theory (DFT) calculations reveal that the isolated bond-shrinking low-valence Cu (+1)–N 4 –C 8 S 2 atomic interface moiety serves as an active site during the ORR process, and the synergistic mechanism between the Cu species and the carbon matrix at the atomic interface plays a critical role in boosting the ORR efficiency, by adjusting the reaction free energy of intermediate adsorption. Furthermore, this atomic interface concept may provide an alternative methodology for the rational design of advanced oxygen electrode materials and new probability to improve their catalytic performance.
An atomic beam of titanium for ultracold atom experiments
Here we generate an atomic beam of titanium (Ti) using a “Ti-ball” Ti-sublimation pump, which is a common getter pump used in ultrahigh vacuum systems. We show that the sublimated atomic beam can be optically pumped into the metastable 3d 3 ( 4 F)4s a 5 F 5 state, which is the lower energy level in a cycling optical transition that can be used for laser cooling. We measure the atomic density and transverse and longitudinal velocity distributions of the beam through laser fluorescence spectroscopy. We find a metastable atomic flux density of 4.3(2) × 10 9 s -1 cm -2 with a mean forward velocity of 773(8) m/s at 2.55 cm directly downstream of the center of the Ti-ball. Owing to the details of optical pumping, the beam is highly collimated along the transverse axis parallel to the optical pumping beam and the flux density falls off as 1/r. We discuss how this source can be used to load atoms into a magneto-optical trap.
Elemental and lattice-parameter mapping of binary oxide superlattices of (LaNiO 3 ) 4 /(LaMnO 3 ) 2 at atomic resolution
We construct the elemental distribution and lattice strain maps from the measured atomic column positions in a (LaNiO3)(4)/(LaMnO3)(2) superlattice over a large field of view. The correlation between the distribution of B-cations and the lattice parameter in the form of Vegard's law is validated using atomic resolution energy dispersive x-ray spectroscopy (EDS). The maps show negligible Mn intermixing in the LaNiO3 layer, while Ni intermixing in the LaMnO3 layer improves away from the substrate interface to 9.5 atomic% from the 8th period onwards, indicating that the superlattice interfacial sharpness is established as the distance from the substrate increases. The maps allow an observation of the compositional defects of the B-sites, which is not possible by Z-contrast alone. Thus, this study demonstrates a promising approach for atomic scale correlative study of lattice strain and composition, and a method for the calibration of atomic resolution EDS maps.
Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation
To improve fuel efficiency, advanced combustion engines are being designed to minimize the amount of heat wasted in the exhaust. Hence, future generations of catalysts must perform at temperatures that are 100°C lower than current exhaust-treatment catalysts. Achieving low-temperature activity, while surviving the harsh conditions encountered at high engine loads, remains a formidable challenge. In this study, we demonstrate how atomically dispersed ionic platinum (Pt 2+ ) on ceria (CeO 2 ), which is already thermally stable, can be activated via steam treatment (at 750°C) to simultaneously achieve the goals of low-temperature carbon monoxide (CO) oxidation activity while providing outstanding hydrothermal stability. A new type of active site is created on CeO 2 in the vicinity of Pt 2+ , which provides the improved reactivity. These active sites are stable up to 800°C in oxidizing environments.
Towards resolving protein structures at the atomic scale using atom probe tomography
In the field of Structural Biology, Atom Probe Tomography (APT) is in the nascent stages of development wherein coarse-grained visuals of proteins have been captured. The characterization of organic samples or biomolecules through the technique is currently limited to the detection of a few dominant signatures. The problem of indecipherable characterization can inherently be traced back to multiple forms of technique-specific responses to organic samples and consequent triggers leading to organic-sample and sample-medium interactions. While it is possible for captured manifestations of protein reconstructions to seemingly appear intact from a basic visual purview, the parameter-protein associative responses throughout the structure as a direct consequence of the inherent workings of the technique (until harmonized with organic sample complexity and behavior) and field evaporation-based factors make non-aberrative atomic associations infeasible. The work focused on identifying and theorizing the (above stated and other) fundamental mechanisms that stronghold the study of intricate atomic to higher order associations in proteins through APT. Attempts at structure elucidation of the cryogenic sample under study, through indirect associations (and methods) based on other imaging techniques, further revealed the distinct and highly distortive nature at the atomic scale deterring structural tunability and thus characterization of APT based cryogenic samples under analysis. As a direct counter to the atomic scale characterization problem, by taking the experiment-specific uncertainties, and probable APT-centric organic sample-based variabilities into account, a basic result is extracted and presented. Through mass-spectrometric and computational analysis, specific individual amino acids (Sulfur-containing protein-bound amino acids) in proteins and aspects of protein structure (probable backbone fragments, partial sequence - partial backbone portions) have been identified and characterized. Under analysis considerations, a few of the simplest known and easily inferable segments that favor structural deteriorations in the reconstructions are stated. Additionally, to overcome technique-specific deterrents to the characterization of biomolecules in cryogenic sample medium, the development of a protein-labeling strategy tailored to APT is suggested.
Combustor exhaust-emissions and blowout-limits with diesel number 2 and jet A fuels utilizing air-atomizing and pressure atomizing nozzles
Experimental tests with diesel number 2 and Jet A fuels were conducted in a combustor segment to obtain comparative data on exhaust emissions and blowout limits. An air-atomizing nozzle was used to inject the fuels. Tests were also made with diesel number 2 fuel using a pressure-atomizing nozzle to determine the effectiveness of the air-atomizing nozzle in reducing exhaust emissions. Test conditions included fuel-air ratios of 0.008 to 0.018, inlet-air total pressures and temperatures of 41 to 203 newtons per square centimeter and 477 to 811 K, respectively, and a reference velocity of 21.3 meters per second. Smoke number and unburned hydrocarbons were twice as high with diesel number 2 as with Jet A fuel. This was attributed to diesel number 2 having a higher concentration of aromatics and lower volatility than Jet A fuel. Oxides of nitrogen, carbon monoxide, and blowout limits were approximately the same for the two fuels. The air-atomizing nozzle, as compared with the pressure-atomizing nozzle, reduced oxides-of-nitrogen by 20 percent, smoke number by 30 percent, carbon monoxide by 70 percent, and unburned hydrocarbons by 50 percent when used with diesel number 2 fuel.
Interactions of satellite-speed helium atoms with satellite surfaces. 2: Energy distributions of reflected helium atoms
Energy transfer in collisions of satellite-speed (7,000 m/sec) helium atoms with a cleaned 6061-T6 satellite-type aluminum surface was investigated using the molecular-beam technique. The amount of energy transferred was determined from the measured energy of the molecular-beam and the measured spatial and energy distributions of the reflected atoms. Spatial distributions of helium atoms scattered from a 6061-T6 aluminum surface were measured. The scattering pattern exhibits a prominent backscattering, probably due to the gross surface roughness and/or the relative lattice softness of the aluminum surface. Energy distributions of reflected helium atoms from the same surface were measured for six different incidence angles. For each incidence angle, distributions were measured at approximately sixty scattering positions. At a given scattering position, the energy spectra of the reflected helium atoms and the background gas were obtained using the retarding-field energy analyzer.