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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Carbonaceous spheres—an unusual template for solid metal oxide mesoscale spheres: Application to ZnO spheres

A green template route for the synthesis of mesoscale solid ZnO spheres was ascertained. The protocol involves a double coating of the carbonaceous spheres with successive layers of zinc-containing species by alternating a non-ultrasound and ultrasound-assisted deposition, followed by calcination treatments. The composites were characterized by FTIR spectroscopy, thermal analysis, scanning electron microscopy while the obtained ZnO spheres by X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, N{sub 2} adsorption–desorption isotherms and photoluminescence investigations. A growth mechanism of the solid spheres is advanced based on these results. While the spheres' diameters and the mean size values of ZnO are independent on deposition order, the surface area and the external porosity are fairly dependent. The photoluminescence measurements showed interesting emission features, with emission bands in the violet to orange region. The spheres present high photocatalytical activity towards the degradation of phenol under UV irradiation, the main reaction being its mineralization. - Graphical abstract: A novel and eco-friendly methodology for the synthesis of mesoscale solid ZnO spheres was developed. The protocol involves a double coating of the starch-derived carbonaceous spheres with successive layers of zinc-containing species by alternating a non-ultrasound and ultrasound-assisted deposition, followed by calcination treatments. - Highlights: • ZnO solid spheres are obtained via a template route using carbonaceous spheres. • Two-step coatings of interchangeable order are used as deposition procedure. • The coating procedure influences the porosity and surface area. • ZnO spheres exhibited interesting visible photoluminescence properties. • Solid spheres showed photocatalytical activity in degradation of phenol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis and characterization of hollow mesoporous BaFe{sub 12}O{sub 19} spheres

A facile method is reported to synthesize hollow mesoporous BaFe{sub 12}O{sub 19} spheres using a template-free chemical etching process. Hollow BaFe{sub 12}O{sub 19} spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 °C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. - Graphical abstract: Hollow spherical BaFe{sub 12}O{sub 19} particles are polycrystalline with both grains and grain boundaries. Grain boundaries have less ordered structure and lower stability. When the particles are exposed to high temperature alkaline ethylene glycol, the grain boundaries are etched, leaving small grooves between grains. These grooves allow ethylene glycol to diffuse inside to further etch the grains. As the grain size decreases, gaps appear on the particle surfaces, and a porous structure is finally formed. - Highlights: • Two-step synthesis method for hollow mesoporous BaFe{sub 12}O{sub 19} spheres is proposed. • Porosity of the product can be regulated by controlling the second step of chemical etching. • The crystal structure and magnetic properties are examined to be little affected during the chemical etching. • The mesoporous structure formation mechanism is explained by grain boundary etching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

A series of heteroleptic 17e- cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), [CpC5F4NCoII(PtBu2NPh2)](BF4), [where P2tBuN2Ph = 1,5-diphenyl-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)] were synthesized, and structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)] as a result of the strongly electron-withdrawing perfluorpyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e- complexes CpICo(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the cobalt hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4). The cobalt hydride with the most electron-withdrawing Cp ligand, [CpC5F4NCoIII(PtBu2NPh2)H]+ is an electrocatalyst for production of H2 using 4-MeOC6H4NH3BF4 (pKaMeCN = 11.86) with a turnover frequency of 350 s-1 and an overpotential of 0.75 V. Experimental measurement of thermochemical data provided further insights into the thermodynamics of H2 elimination. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

hydrogen, catalysis, electrocatalysis, proton rela↗
DOE OSTI2014

Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation

Hydrogenase enzymes provide inspiration for investigations of molecular catalysts utilizing structural and functional mimics of the active site. However, the resulting active site mimics cannot match the combination of high rates and low overpotentials of the enzyme, suggesting that the rest of the protein scaffold, i.e., the outer coordination sphere, is necessary for the efficiency of hydrogenase. Therefore, inclusion of outer coordination sphere elements onto molecular catalysts may enable us to achieve and ultimately surpass the overall enzymatic efficiency. In an effort to identify and include the missing enzymatic features, there has been recent effort to understand the effect of outer coordination sphere elements on molecular catalysts for hydrogen oxidation and production. Our focus has been to utilize amino acid or peptide based scaffolds on an active functional mimic for hydrogen oxidation and production, [Ni(PR2NR’2)2]2+. This bottom-up approach, i.e, building an outer coordination sphere around a functional molecular catalyst, has allowed us to evaluate individual contributions to catalysis, including enhancing proton movement, concentrating substrate and introducing structural features to control reactivity. Collectively, these studies have resulted in catalysts that can operate faster, can operate at lower overpotentials, have enhanced water solubility, and/or can provide more stability to oxygen or extreme conditions such as strongly acidic or basic conditions than their unmodified parent complexes. Common mechanisms have yet to be defined to predictably control these processes but our growing knowledge in this area is essential for the eventual mimicry of enzymes for developing efficient molecular catalysts for practical use. This account reviews previously published work supported by the US DOE Basic Energy Sciences (BES), Physical Bioscience program, the Office of Science Early Career Research Program through the USDOE, BES, the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, Office of Science, Office of BES. Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. DOE’s Office of Biological and Environmental Research program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

bioinspired↗
DOE OSTI2014

Enzyme Design From the Bottom Up: An Active Nickel Electrocatalyst with a Structured Peptide Outer Coordination Sphere

Functional, peptide-containing metal complexes with a well-defined peptide structure have the potential to enhance molecular catalysts via an enzyme-like outer coordination sphere. Here, we report the synthesis and characterization of an active, peptide-based metal complex built upon the well characterized hydrogen production catalyst, Ni(PPh2NPh)2. The incorporated peptide maintains its B-hairpin structure when appended to the metal core, and the electrocatalytic activity of the peptide-based metal complex (~100,000 s-1) is fully retained. The combination of an active molecular catalyst with a structured peptide outer coordination sphere provides a scaffold that permits the incorporation of features of an enzyme-like outer-coordination sphere necessary to create molecular electrocatalysts with en-hanced functionality.

bioinspired↗
DOE OSTI2015

Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay

Oxidation of hydrogen (H₂) to protons and electrons for energy production in fuel cells is catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton delivery and removal is critical in hydrogenase enzymes in nature that catalyze H₂ oxidation using earth-abundant metals (iron and nickel). Here we report a synthetic iron complex, (Cp C 5 F 4 N )Fe(P Et N (CH 2 ) 3 NMe 2 PEt)(Cl), that serves as a precatalyst for the oxidation of H₂, with turnover frequencies of 290 s⁻¹ in fluorobenzene, under 1 atm of H₂ using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the exogenous base. The cooperative effect of the primary, secondary and outer coordination spheres for moving protons in this remarkably fast catalyst emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Synthesis of Nitrogen-Doped Mesoporous Carbon Spheres with Extra-Large Pores through Assembly of Diblock Copolymer Micelles

In this study, the synthesis of highly nitrogen-doped mesoporous carbon spheres (NMCS) is reported. The large pores of the NMCS were obtained through self-polymerization of dopamine (DA) and spontaneous co-assembly of diblock copolymer micelles. The resultant narrowly dispersed NMCS possess large mesopores (ca. 16 nm) and small particle sizes (ca. 200 nm). Lastly, the large pores and small dimensions of the N-heteroatom-doped carbon spheres contribute to the mass transportation by reducing and smoothing the diffusion pathways, leading to high electrocatalytic activity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Examining astrophysical gas cloud collapse using an optical depth-scaled, x-ray-irradiated, carbon-foam sphere

When stellar radiation interacts with a molecular cloud, the cloud's fate depends on the strength of the incident radiation and the radiation's mean-free-path within the cloud [F. Bertoldi, Astrophys. J. 346, 735–755 (1989)]. Under the right conditions, the radiation compresses the cloud and a star formation may occur. Where and when the stellar formation occurs in the cloud's collapse are open questions. Direct observation of the complete star–cloud lifecycle is nearly impossible due to the immense timescales and distances over which the interaction occurs. Laboratory astrophysics offers a way to investigate such a system by scaling the important astrophysical parameters to the laboratory. This work describes laboratory experiments to study the radiation-driven implosion of clouds, using x rays from a laser-irradiated, thin, gold foil as a surrogate star and a carbon-foam sphere as a surrogate cloud. An optically thick system, theoretically corresponding to a star-forming regime, was selected by choice of the foam density. Gold foil and sphere motions were imaged by x-ray radiography. Radiographic images show the formation of an interface between rarefied gold and carbon plasmas, a shock moving into the sphere, and a blunting of the initial sphere's shape. Measurements show that the shock moved linearly around 64 μm/ns into the sphere, and the gold–carbon interface formed by 2 ns at the sphere edge remained stationary. The deformation of the sphere was driven by the incident radiation and not by mechanical pressures applied by gold plasma. The blunting of the sphere was likely due to the geometric reduction of flux near the sphere's poles. Higher x-ray flux near the sphere's equator caused high compression and a faster shock, which flattened the sphere. We will discuss the results and implications of our observations.

VanDervort, R. W. [University of Michigan 1 , Ann ↗
DOE OSTI2016

Cavitation and radicals drive the sonochemical synthesis of functional polymer spheres

Sonochemical synthesis can lead to a dramatic increase in the kinetics of formation of polymer spheres (templates for carbon spheres) compared to the modified Stöber silica method applied to produce analogous polymer spheres. Reactive molecular dynamics simulations of the sonochemical process indicate a significantly enhanced rate of polymer sphere formation starting from resorcinol and formaldehyde precursors. The associated chemical reaction kinetics enhancement due to sonication is postulated to arise from the localized lowering of atomic densities, localized heating, and generation of radicals due to cavitation collapse in aqueous systems. This dramatic increase in reaction rates translates into enhanced nucleation and growth of the polymer spheres. The results are of broad significance to understanding mechanisms of sonication induced synthesis as well as technologies utilizing polymers spheres.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Capillary spreading of contact line over a sinking sphere

The contact line dynamics over a sinking solid sphere are investigated in comparison with classical spreading theories. Experimentally, high-speed imaging systems with optical light or x-ray illumination are employed to accurately measure the spreading motion and dynamic contact angle of the contact line. Millimetric spheres are controlled to descend with a constant speed ranging from 3.2 x 10 4 to 0.79 m/s. We observed three different spreading stages over a sinking sphere, which depends on the contact line velocity and contact angle. These stages consistently showed the characteristics of capillarity-driven spreading as the contact line spreads faster with a higher contact angle. The contact line velocity is observed to follow a classical capillary-viscous model at a higher Ohnesorge number (> 0.02). For the cases with a relatively low Ohnesorge number (< 0.02), the contact line velocity is significantly lower than the speed predicted by the capillary-viscous balance. This indicates the existence of an additional opposing force (inertia), which is a similar transition from capillary viscous to capillary-inertia balances found in drop-impact dynamics. Additionally, we observed the linear relation between the contact line velocity and the sphere sinking speed during the second stage, in which the contact line inertia is balanced with the impact pressure by a sphere at high inertia regimes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Facile synthesis and microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere and multi-shelled NiO hollow sphere

We reported the preparation of C@Ni–NiO core–shell hybrid solid spheres or multi-shelled NiO hollow spheres by combining a facile hydrothermal route with a calcination process in H{sub 2} or air atmosphere, respectively. The synthesized C@Ni–NiO core–shell solid spheres with diameters of approximately 2–6 μm were in fact built from dense NiO nanoparticles coated by random two-dimensional metal Ni nanosheets without any visible pores. The multi-shelled NiO hollow spheres were built from particle-like ligaments and there are a lot of pores with size of several nanometers on the surface. Combined Raman spectra with X-ray photoelectron spectra (XPS), it suggested that the defects in the samples play a limited role in the dielectric loss. Compared with the other samples, the permeability of the samples calcined in H{sub 2} and air was increased slightly and the natural resonance frequency shifted to higher frequency (7, 11 and 14 GHz, respectively), leading to an enhancement of microwave absorption property. For the sample calcined in H{sub 2}, an optimal reflection loss less than − 10 was obtained at 7 GHz with a matching thickness of 5.0 mm. Our study demonstrated the potential application of C@Ni–NiO core–shell hybrid solid sphere or multi-shelled NiO hollow sphere as a more efficient electromagnetic (EM) wave absorber. - Highlights: • C@Ni–NiO core–shell hybrid solid sphere was synthesized by a facile method. • Multi-shelled NiO hollow sphere was synthesized by a facile method. • It suggested that the defects in the samples play a limited role in dielectric loss. • The permeability of the samples calcined in H{sub 2} and air was increased. • Microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere was investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evaluation of Polyethylene and Blank Pulsed Sphere Experiments Using Deuteron Transport Feature in COG

From the late 1960s to about 1985, LLNL undertook a series of ‘pulsed sphere’ experiments for 31 materials involving 148 different experiments using 75 different spheres. The purpose was to measure the neutron leakage spectra for different materials from 14-MeV neutrons generated by 3 H(d,n) 4 He reactions induced by an incident D+ beam from the Insulated Core Transfer (ICT) accelerator at LLNL. This deuteron beam was focused to impinge upon tritium loaded onto a titanium substrate within a low mass target assembly placed within the center of a spherical shell constructed from the material of interest. COG is a three-dimensional, continuous energy, Monte Carlo code, developed by Lawrence Livermore National Laboratory (LLNL). Recent additions to COG include alpha and deuteron particle transport in order to directly calculate (α,n) and 3 H(d,n) 4 He reactions, and resulting neutron emission spectra. Results of the direct deuteron transport calculation for the 0.8 MFP (mean free path) polyethylene sphere with PILOT B detector was previously published. The purpose of this paper is to present expanded COG results showing the neutron peak from deuterium buildup ( 2 H(d,n) 3 He) due to tritium decay in the target. Cross section data libraries used are ENDF/B-VIII.0 for neutrons and ENDF/B-VII.1 for deuterons, respectively.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

In Situ Real-Time Radiographic Study of Thin Film Formation Inside Rotating Hollow Spheres

Hollow spheres with uniform coatings on the inner surface have applications in optical devices, time- or site controlled drug release, heat storage devices, and target fabrication for inertial confinement fusion experiments. The fabrication of uniform coatings, which is often critical for the application performance, requires precise understanding and control over the coating process and its parameters. Here, we report on in-situ real-time radiography experiments that provide critical spatio-temporal information about the distribution of fluids inside hollow spheres during uniaxial rotation. Image analysis and computer fluid dynamics simulations were used to explore the effect of liquid viscosity and rotational velocity on the film uniformity. The data were then used to demonstrate the fabrication of uniform sol-gel chemistry derived porous polymer films inside 2mm inner diameter diamond shells.

aerogel↗