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All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Toward Edge-Defined Holey Boron Nitride Nanosheets

"Holey" two-dimensional (2D) nanosheets with well-defined holy morphology and edge chemistry are highly desirable for applications such as energy storage, catalysis, sensing, transistors, and molecular transport/separation. For example, holey grapheme is currently under extensive investigation for energy storage applications because of the improvement in ion transport due to through the thickness pathways provided by the holes. Without the holes, the 2D materials have significant limitations for such applications in which efficient ion transport is important. As part of an effort to apply this approach to other 2D nanomaterials, a method to etch geometrically defined pits or holes on the basal plane surface of hexagonal boron nitride (h-BN) nanosheets has been developed. The etching, conducted via heating in ambient air using metal nanoparticles as catalysts, was facile, controllable, and scalable. Starting h-BN layered crystals were etched and subsequently exfoliated into boron nitride nanosheets (BNNSs). The as-etched and exfoliated h-BN nanosheets possessed defined pit and hole shapes that were comprised of regulated nanostructures at the edges. The current finding are the first step toward the bulk preparation of holey BNNSs with defined holes and edges.

Lin, Yi↗
NASA NTRS1983

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10 to the 10th molecules (a fraction of a monolayer) on a 1 sq mm junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing.

Khanna, S. K.↗
NASA NTRS1989

Mars, clays and the origins of life

To detect life in the Martian soil, tests were designed to look for respiration and photosynthesis. Both tests (labeled release, LR, and pyrolytic release, PR) for life in the Martian soils were positive. However, when the measurement for organic molecules in the soil of Mars was made, none were found. The interpretation given is that the inorganic constituents of the soil of Mars were responsible for these observations. The inorganic analysis of the soil was best fitted by a mixture of minerals: 60 to 80 percent clay, iron oxide, quartz, and soluble salts such as halite (NaCl). The minerals most successful in simulating the PR and LR experiments are iron-rich clays. There is a theory that considers clays as the first organisms capable of replication, mutation, and catalysis, and hence of evolving. Clays are formed when liquid water causes the weathering of rocks. The distribution of ions such as aluminum, magnesium, and iron play the role of bases in the DNA. The information was stored in the distribution of ions in the octahedral and tetrahedral molecules, but that they could, like RNA and DNA, replicate. When the clays replicated, each sheet of clay would be a template for a new sheet. The ion substitutions in one clay sheet would give rise to a complementary or similar pattern on the clay synthesized on its surface. It was theorized that it was on the surface of replicating iron-rich clays that carbon dioxide would be fixed in the light into organic acids such as formic or oxalic acid. If Mars had liquid water during a warm period in its past, clay formation would have been abundant. These clays would have replicated and evolved until the liquid water was removed due to cooling of Mars. It is entirely possible that the Viking mission detected life on Mars, but it was clay life that awaits the return of water to continue its evolution into life based on organic molecules.

Hartman, Hyman↗
NASA NTRS2003

Carbon Nanotube Synthesis in a Flame with Independently Prepared Laser-Ablated Catalyst Particles

Laser ablation has been used ex situ to create metal nanoparticles for introduction into a reactive pyrolysis flame. By prior synthesis of the metal nanoparticles, the effects of the reactive gases can be clearly separated from the pyrolysis chemistry of a solvent carrier, as when nebulized solutions are used. Moreover, varying reactivity issues associated with particle growth and size are bypassed. Our results show that Fe selectively reacts with CO to produce nanotubes, whereas Ni selectively reacts with C2H2 to produce nanofibers. These observations are interpreted through the donation and withdrawal of electron density between the adsorbate's molecular orbitals and surface atoms of the metal nanoparticle. The rate of reaction of Ni with only C2H2 is found to be greater than the rate with C2H2 and CO. This suggests that CO inhibits the Ni-catalyzed reaction.

Nanotubes, Carbon/chemistry/ultrastructure↗
NASA NTRS1983

Surface studies with (clean) supported metal particles and clusters

Small particles are ideal for combined studies with surface analytical and electron microscopy/diffraction methods. In this way crystallography, microstructure, morphology, physical stability, and electronic structure can be correlated directly with chemical reactivity. Various integrated experimental approaches for conducting model studies with UHV-evaporated particles have been successfully developed; they entail the use of TPD, AES, XPS, and work function measurements on one hand and standard TEM/TED, in-situ TEM/TED, and in-situ STED/TEM techniques on the other hand. The essential features of four particular experimental approaches are discussed and a selection of representative results is presented to illustrate the potential usefulness of such studies in the field of catalysis.

Poppa, H. R.↗
NASA NTRS1991

Surface activation of air oxidation of hydrazine on kaolinite. 2. Consideration of oxidizing/reducing entities in relationship to other compositional, structural, and energetic factors

The rates (previously reported) for the air oxidation of hydrazine on kaolinite and substituent oxides of kaolinite showed a complex dependence on the relative amounts of several structural oxidizing/reducing entities within the reaction-promoting solids. The rates indicated an important role of the clay but no dominant role of any one of the oxidizing/reducing entities. In this paper we review (a) the reaction-promoting activity of these centers as studied in other systems, (b) various spectroscopic results showing interaction between these entities in clays, and (c) reported spectroscopic studies of the complexation between hydrazine and aluminosilicate surfaces as a whole, in an effort to propose a mechanism for the reaction. Whereas some uncertainties remain, the present synthesis concludes that a mechanism operating through single electron/hole transfers and hydrogen atom transfers by discrete centers is adequate to explain the observed rate behaviors including the observed second order dependence of the oxidation rate on catalyst amount. The effects of these operations on the catalyst can result in no alteration of, or complete or partial electronic relaxation of its contingent of trapped separated charge pairs. The degree to which surface complexation as a whole, intercalation, or luminescent processes may also be associated with the reaction cannot be adequately assessed with the information in hand.

NASA Program Exobiology↗
NASA NTRS1994

Stability of the Martian atmosphere: Is heterogeneous catalysis essential?

A comprehensive homogeneous gas phase photochemical model is developed to study the problem of stability of the Martian atmosphere. The one-dimensional model extends from the ground up to 220 km, passing through the homopause at 125 km. The model thus couples the lower (neutral) atmosphere to the ionosphere above which provides significant downward flux of carbon monoxide and oxygen atoms. It is concluded on the basic of currently accepted values for globally and seasonally averaged water vapor abundance, dust opacity and the middle atmospheric eddy mixing coefficient, as well as the relevant laboratory data (particularly the temperature dependence of CO2 absorption cross section and the rate constant for CO+OH reaction), that the rate of re-formation of carbon dioxide exceeds its photolytic destruction rate by about 40%. Furthermore, it is found that this result is virtually independent of the choice of eddy mixing coefficient, unless its value in the middle atmosphere exceeds 10(exp 8) sq cm/sec or is far smaller than 10(exp 5)sq cm/sec, or the dust opacity, unless it exceeds unity, or the water vapor mixing ratio at the surface, unless it is far smaller (less than or = 1 ppm) or far greater (greater than or = 500 ppm) than the average value (approximately 150 ppm). Since none of these extremes represent globally and seasonally averaged conditions on Mars, we propose that the present model requires existence of a mechanism to throttle down the recycling rate of carbon dioxide on Mars. Therefore, it is suggested that a heterogeneous process which provides a sink to the species that participate in the recycling of CO2, i.e., H2O, H2O2, OH, CO or O, in particular, may be necessary to bring about the balance between the CO2 recycling rate and its photolytic destruction rate. Aerosols of dust or ice (pure or doped water or carbon dioxide ice present in the atmosphere of Mars) can provide the appropriate adsorption sites for the above heterogeneous process. Despite our conclusion that some heterogeneous process may be needed, it is important to recognize that one-dimensional models can only provide first-order results which, most likely, represent globally and seasonally averaged conditions. However, it is only after actual temporal, latitudinal and longitudinal variations of relevant atmospheric parameters are included in the model that one can determine fuly whether the problem of atmospheric stabiltiy still continues to persist and whether some heterogeneous process is required to correct it.

Atreya, Sushil K.↗
NASA NTRS2004

Gas-phase production of single-walled carbon nanotubes from carbon monoxide: a review of the hipco process

The latest process for producing large quantities of single-walled carbon nanotubes (SWNTs) to emerge from the Rice University, dubbed HiPco, is living up to its promise. The current production rates approach 450 mg/h (or 10 g/day), and nanotubes typically have no more than 7 mol % of iron impurities. Second-generation HiPco apparatus can run continuously for 7-10 days at a time. In the HiPco process nanotubes grow in high-pressure, high-temperature flowing CO on catalytic clusters of iron. Catalyst is formed in situ by thermal decomposition of iron pentacarbonyl, which is delivered intact within a cold CO flow and then rapidly mixed with hot CO in the reaction zone. Upon heating, the Fe(CO)5 decomposes into atoms that condense into larger clusters. SWNTs nucleate and grow on these particles in the gas phase via CO disproportionation: CO + CO --> CO2 + C (SWNT), catalyzed by the Fe surface. The concentration of CO2 produced in this reaction is equal to that of carbon and can therefore serve as a useful real-time feedback parameter. It was used to study and optimize SWNT production as a function of temperature, pressure, and Fe(CO)5 concentration. The results of the parametric study are in agreement with current understanding of the nanotube formation mechanism.

Review↗
NASA NTRS1990

Reactivity of pi-complexes of Ti, V, and Nb towards dithioacetic acid: Synthesis and structure of novel metal sulfur-containing complexes

In order to use sulfur-containing resources economically and with minimal environmental damage, it is important to understand the desulfurization processes. Hydrodesulfurization, for example, is carried out on the surface of a heterogeneous metal sulfide catalyst. Studies of simple, soluble inorganic systems provide information regarding the structure and reactivity of sulfur-containing compounds with metal complexes. Further, consistent with recent trends in materials chemistry, many model compounds warrant further study as catalyst precursors. The reactivity of low-valent organometallic sandwich pi-complexes toward dithiocarboxylic acids is described. For example, treatment of bisbenzene vanadium with CH3CSSH affords a divanadium tetrakis(dithioacetate) complex. The crystallographically determined V-V bond distance, 2.800(2), is nearly the same as the V-V bond distance in a V(mu-nu squared-S2)2V' unit in the mineral patonite (VS4)n. The stability of the V2S4 core in the dimer is demonstrated by evidence of V2S4(+) in the mass spectrum (70 eV, solid probe) of the vanadium dimer. Several other systems relevant to HDS catalysis are also discussed.

Duraj, Stan A.↗
NASA NTRS2015

In-Situ Resource Utilization for Space Exploration: Resource Processing, Mission-Enabling Technologies, and Lessons for Sustainability on Earth and Beyond

As humanity begins to reach out into the solar system, it has become apparent that supporting a human or robotic presence in transit andor on station requires significant expendable resources including consumables (to support people), fuel, and convenient reliable power. Transporting all necessary expendables is inefficient, inconvenient, costly, and, in the final analysis, a complicating factor for mission planners and a significant source of potential failure modes. Over the past twenty-five years, beginning with the Space Exploration Initiative, researchers at the NASA Glenn Research Center (GRC), academic collaborators, and industrial partners have analyzed, researched, and developed successful solutions for the challenges posed by surviving and even thriving in the resource limited environment(s) presented by near-Earth space and non-terrestrial surface operations. In this retrospective paper, we highlight the efforts of the co-authors in resource simulation and utilization, materials processing and consumable(s) production, power systems and analysis, fuel storage and handling, propulsion systems, and mission operations. As we move forward in our quest to explore space using a resource-optimized approach, it is worthwhile to consider lessons learned relative to efficient utilization of the (comparatively) abundant natural resources and improving the sustainability (and environment) for life on Earth. We reconsider Lunar (and briefly Martian) resource utilization for potential colonization, and discuss next steps moving away from Earth.

Specific impulse↗
NASA NTRS2020

Polycyclic Aromatic Hydrocarbons and Dust Particle Surface Interactions: Catalytic Hydrogenation of Polycyclic Aromatic Hydrocarbon Molecules under Vacuum Conditions

This work reports experiments on the catalytic interaction occurring between polycyclic aromatic hydrocarbon (PAH) molecules and TiO2 dust grain surfaces under vacuum conditions. The investigation sheds light on the potential catalytic pathways that TiO2 dust surfaces provide in the hydrogenation of PAH molecules and the chemistry that can be driven by PAH-dust interactions under vacuum conditions. Naphthalene, anthracene, and coronene were chosen as the PAH molecules, while titanium dioxide was selected as the dust analog. PAH samples and dust analog mixtures were studied under vacuum for 24 h while monitored via diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The acquired spectra show that PAH molecules are hydrogenated when in contact with TiO2 dust particles without the need for external energy or hydrogen sources. Our results suggest that linear PAHs undergo a similar hydrogenation process where the dominant species are fully hydrogenated PAHs. For larger condensed PAHs, the hydrogenation process yields partially hydrogenated molecules. Fully hydrogenated species can be identified by a band around 2960 per cm, while partially hydrogenated species produce a band around 2825 per cm. In the case of the production of hydrogenated species, our results suggest that the smaller the PAH, the faster the hydrogenation rate.

polycyclic aromatic hydrocarbons↗
NASA NTRS2011

Catalytic Microtube Rocket Igniter

Devices that generate both high energy and high temperature are required to ignite reliably the propellant mixtures in combustion chambers like those present in rockets and other combustion systems. This catalytic microtube rocket igniter generates these conditions with a small, catalysis-based torch. While traditional spark plug systems can require anywhere from 50 W to multiple kW of power in different applications, this system has demonstrated ignition at less than 25 W. Reactants are fed to the igniter from the same tanks that feed the reactants to the rest of the rocket or combustion system. While this specific igniter was originally designed for liquid methane and liquid oxygen rockets, it can be easily operated with gaseous propellants or modified for hydrogen use in commercial combustion devices. For the present cryogenic propellant rocket case, the main propellant tanks liquid oxygen and liquid methane, respectively are regulated and split into different systems for the individual stages of the rocket and igniter. As the catalyst requires a gas phase for reaction, either the stored boil-off of the tanks can be used directly or one stream each of fuel and oxidizer can go through a heat exchanger/vaporizer that turns the liquid propellants into a gaseous form. For commercial applications, where the reactants are stored as gases, the system is simplified. The resulting gas-phase streams of fuel and oxidizer are then further divided for the individual components of the igniter. One stream each of the fuel and oxidizer is introduced to a mixing bottle/apparatus where they are mixed to a fuel-rich composition with an O/F mass-based mixture ratio of under 1.0. This premixed flow then feeds into the catalytic microtube device. The total flow is on the order of 0.01 g/s. The microtube device is composed of a pair of sub-millimeter diameter platinum tubes connected only at the outlet so that the two outlet flows are parallel to each other. The tubes are each approximately 10 cm long and are heated via direct electric resistive heating. This heating brings the gasses to their minimum required ignition temperature, which is lower than the auto-thermal ignition temperature, and causes the onset of both surface and gas phase ignition producing hot temperatures and a highly reacting flame. The combustion products from the catalytic tubes, which are below the melting point of platinum, are injected into the center of another combustion stage, called the primary augmenter. The reactants for this combustion stage come from the same source but the flows of non-premixed methane and oxygen gas are split off to a secondary mixing apparatus and can be mixed in a near-stoichiometric to highly lean mixture ratio. The primary augmenter is a component that has channels venting this mixed gas to impinge on each other in the center of the augmenter, perpendicular to the flow from the catalyst. The total crosssectional area of these channels is on a similar order as that of the catalyst. The augmenter has internal channels that act as a manifold to distribute equally the gas to the inward-venting channels. This stage creates a stable flame kernel as its flows, which are on the order of 0.01 g/s, are ignited by the combustion products of the catalyst. This stage is designed to produce combustion products in the flame kernel that exceed the autothermal ignition temperature of oxygen and methane.

Schneider, Steven J.↗
NASA NTRS2009

Continuous Lidar Monitoring of Polar Stratospheric Clouds at the South Pole

Polar stratospheric clouds (PSC) play a primary role in the formation of annual ozone holes over Antarctica during the austral sunrise. Meridional temperature gradients in the lower stratosphere and upper troposphere, caused by strong radiative cooling, induce a broad dynamic vortex centered near the South Pole that decouples and insulates the winter polar airmass. PSC nucleate and grow as vortex temperatures gradually fall below equilibrium saturation and frost points for ambient sulfate, nitrate, and water vapor concentrations (generally below 197 K). Cloud surfaces promote heterogeneous reactions that convert stable chlorine and bromine-based molecules into photochemically active ones. As spring nears, and the sun reappears and rises, photolysis decomposes these partitioned compounds into individual halogen atoms that react with and catalytically destroy thousands of ozone molecules before they are stochastically neutralized. Despite a generic understanding of the ozone hole paradigm, many key components of the system, such as cloud occurrence, phase, and composition; particle growth mechanisms; and denitrification of the lower stratosphere have yet to be fully resolved. Satellite-based observations have dramatically improved the ability to detect PSC and quantify seasonal polar chemical partitioning. However, coverage directly over the Antarctic plateau is limited by polar-orbiting tracks that rarely exceed 80 degrees S. In December 1999, a NASA Micropulse Lidar Network instrument (MPLNET) was first deployed to the NOAA Earth Systems Research Laboratory (ESRL) Atmospheric Research Observatory at the Amundsen-Scott South Pole Station for continuous cloud and aerosol profiling. MPLNET instruments are eye-safe, capable of full-time autonomous operation, and suitably rugged and compact to withstand long-term remote deployment. With only brief interruptions during the winters of 2001 and 2002, a nearly continuous data archive exists to the present.

OZONE DESTRUCTION↗