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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 91 records · Page 5

Feasibility of Ultraviolet Light Emitting Diodes as an Alternative Light Source for Photocatalysis

The objective of this study was to determine whether ultraviolet light emitting diodes (UV-LEDs) could serve as an alternative photon source efficiently for heterogeneous photocatalytic oxidation (PCO). An LED module consisting of 12 high-power UV-A LEDs was designed to be interchangeable with a UV-A fluorescent black light blue (BLB) lamp in a Silica-Titania Composite (STC) packed bed annular reactor. Lighting and thermal properties were characterized to assess the uniformity and total irradiant output. A forward current of (I(sub F)) 100 mA delivered an average irradiance of 4.0 m W cm(exp -2), which is equivalent to the maximum output of the BLB, but the irradiance of the LED module was less uniform than that of the BLB. The LED- and BLB-reactors were tested for the oxidization of 50 ppmv ethanol in a continuous flow-through mode with 0.94 sec space time. At the same irradiance, the UV-A LED reactor resulted in a lower PCO rate constant than the UV-A BLB reactor (19.8 vs. 28.6 nM CO2 sec-I), and consequently lower ethanol removal (80% vs. 91%) and mineralization efficiency (28% vs. 44%). Ethanol mineralization increased in direct proportion to the irradiance at the catalyst surface. This result suggests that reduced ethanol mineralization in the LED- reactor could be traced to uneven irradiance over the photocatalyst, leaving a portion of the catalyst was under-irradiated. The potential of UV-A LEDs may be fully realized by optimizing the light distribution over the catalyst and utilizing their instantaneous "on" and "off' feature for periodic irradiation. Nevertheless, the current UV-A LED module had the same wall plug efficiency (WPE) of 13% as that of the UV-A BLB. These results demonstrated that UV-A LEDs are a viable photon source both in terms of WPE and PCO efficiency.

Levine, Langanf H.↗

Photochemistry of porphyrins: a model for the origin of photosynthesis

A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

Hydrogen/chemistry↗

Design and assembly of a catalyst bed gas generator for the catalytic decomposition of high concentration hydrogen peroxide propellants and the catalytic combustion of hydrocarbon/air mixtures

A method for designing and assembling a high performance catalyst bed gas generator for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The gas generator utilizes a sectioned catalyst bed system, and incorporates a robust, high temperature mixed metal oxide catalyst. The gas generator requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. The high performance catalyst bed gas generator system has consistently demonstrated high decomposition efficiency, extremely low decomposition roughness, and long operating life on multiple test articles.

Lohner, Kevin A.↗

High Performance Fuel Cell and Electrolyzer Membrane Electrode Assemblies (MEAs) for Space Energy Storage Systems

Regenerative fuel cells provide a pathway to energy storage system development that are game changers for NASA missions. The fuel cell/ electrolysis MEA performance requirements 0.92 V/ 1.44 V at 200 mA/cm2 can be met. Fuel Cell MEAs have been incorporated into advanced NFT stacks. Electrolyzer stack development in progress. Fuel Cell MEA performance is a strong function of membrane selection, membrane selection will be driven by durability requirements. Electrolyzer MEA performance is catalysts driven, catalyst selection will be driven by durability requirements. Round Trip Efficiency, based on a cell performance, is approximately 65%.

Plastic Encapsulated Microelectronics (PEM)↗

Interferences in the chemiluminescent measurement of NO and NO2 emissions from combustion systems

Two factors which may affect the quantification of NO and NO2 concentrations when using chemiluminescent analysis are investigated. The first is the dependence of the chemiluminescent intensity on competing third body quenching reactions. Relative quenching efficiencies are determined as a function of third body concentration for six different species which are common products of combustion. A mathematical expression is derived which allows calculation of the actual concentration of NO given the indicated concentration of NO and the concentrations of the important third bodies. An example calculation is presented. The second factor which is investigated involves the conversion of low molecular weight nitrogen containing species, other than NO2, in commercial NOx converters. Conversion efficiencies for six species were determined using a commercial stainless steel catalyst at 923 K.

Matthews, R. D.↗

Interferences in chemiluminescent measurement of NO and NO2 emissions from combustion systems

Two factors that may affect the quantification of NO and NO2 concentrations when using chemiluminescent analysis are investigated. The first is the dependence of the chemiluminescent intensity on competing third body quenching reactions. Relative quenching efficiencies are determined as a function of third body concentration for six different species that are common products of combustion. A mathematical expression is derived that allows calculation of the actual concentration of NO, given the indicated concentration of NO and the concentrations of the important third bodies. An example calculation is presented. The second factor investigated involves the conversion to NO of low molecular weight nitrogen-containing species, other than NO2, in commercial NOx converters. Conversion efficiencies for six species are determined using a commercial stainless steel catalyst at 920 K.

Matthews, R. D.↗

Evolutionary Cell Computing: From Protocells to Self-Organized Computing

On the path from inanimate to animate matter, a key step was the self-organization of molecules into protocells - the earliest ancestors of contemporary cells. Studies of the properties of protocells and the mechanisms by which they maintained themselves and reproduced are an important part of astrobiology. These studies also have the potential to greatly impact research in nanotechnology and computer science. Previous studies of protocells have focussed on self-replication. In these systems, Darwinian evolution occurs through a series of small alterations to functional molecules whose identities are stored. Protocells, however, may have been incapable of such storage. We hypothesize that under such conditions, the replication of functions and their interrelationships, rather than the precise identities of the functional molecules, is sufficient for survival and evolution. This process is called non-genomic evolution. Recent breakthroughs in experimental protein chemistry have opened the gates for experimental tests of non-genomic evolution. On the basis of these achievements, we have developed a stochastic model for examining the evolutionary potential of non-genomic systems. In this model, the formation and destruction (hydrolysis) of bonds joining amino acids in proteins occur through catalyzed, albeit possibly inefficient, pathways. Each protein can act as a substrate for polymerization or hydrolysis, or as a catalyst of these chemical reactions. When a protein is hydrolyzed to form two new proteins, or two proteins are joined into a single protein, the catalytic abilities of the product proteins are related to the catalytic abilities of the reactants. We will demonstrate that the catalytic capabilities of such a system can increase. Its evolutionary potential is dependent upon the competition between the formation of bond-forming and bond-cutting catalysts. The degree to which hydrolysis preferentially affects bonds in less efficient, and therefore less well-ordered, peptides is also critical to evolution of a non-genomic system. Based on these results, a new computational object called a "molnet" is defined. Like a neural network, it is formed of interconnected units that send "signals" to each other. Like molecules, neural networks have a specific function once their structure is defined. The difference between a molnet and traditional neural networks, is that input to molnets is not simply passed along and processed from input to output units, but rather it is utilized to form and break connections(bonds), and thus to form new structures. Molnets represent a powerful tool that can be used to understand the conditions under which chemical systems can form large molecules, such as proteins, and display ever more complex functions. This has direct applications, for example to the design of smart,synthetic fabrics. Additional information is contained in the original.

Colombano, Silvano↗

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon dioxide-saturated water or bicarbonate solution. The anode side of the cell is supplied with sodium hydroxide solution. The solutions are circulated past the electrodes in the electrochemical cell using pumps. A regulated power supply provides the electrical energy required for the reactions. Photovoltaic cells can be used to better mimic the photosynthetic reaction. The current flowing through the electrochemical cell, and the cell voltage, are monitored during experimentation. The products of the electrochemical reduction of carbon dioxide are allowed to accumulate in the cathode reservoir. Samples of the cathode solution are withdrawn for product analysis. Oxygen is generated on the anode side and is allowed to vent out of the reservoir.

Narayan, Sri↗

Improved Anode for a Direct Methanol Fuel Cell

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Valdez, Thomas↗

Sustainability of the Catalytic Activity of a Silica-Titania Composite (STC) for Long-Term Indoor Air Quality Control

TiO2-assisted photocatalytic oxidation (PCO) is an emerging technology for indoor air quality control and is also being evaluated as an alternative trace contaminant control technology for crew habitats in space exploration. Though there exists a vast range of literature on the development of photocatalysts and associated reactor systems, including catalyst performance and performance-influencing factors, the critical question of whether photocatalysts can sustain their initial catalytic activity over an extended period of operation has not been adequately addressed. For a catalyst to effectively serve as an air quality control product, it must be rugged enough to withstand exposure to a multitude of low concentration volatile organic compounds (VOCs) over long periods of time with minimal loss of activity. The objective of this study was to determine the functional lifetime of a promising photocatalyst - the silica-titania composite (STC) from Sol Gel Solutions, LLC in a real-world scenario. A bench-scale STC-packed annular reactor under continuous irradiation by a UV-A fluorescent black-light blue lamp ((lambda)max = 365 nm) was exposed to laboratory air continuously at an apparent contact time of 0.27 sand challenged with a known concentration of ethanol periodically to assess any changes in catalytic activity. Laboratory air was also episodically spiked with halocarbons (e.g., octafluoropropane), organosulfur compounds (e.g., sulfur hexafluoride), and organosilicons (e.g., siloxanes) to simulate accidental releases or leaks of such VOCs. Total organic carbon (TOC) loading and contaminant profiles of the laboratory air were also monitored. Changes in STC photocatalytic performance were evaluated using the ethanol mineralization rate, mineralization efficiency, and oxidation intermediate (acetaldehyde) formation. Results provide insights to any potential catalyst poisoning by trace halocarbons and organosulfur compounds.

Coutts, Janelle L.↗

Near-ambient solid polymer fuel cell

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Holleck, G. L.↗

Bifunctional alkaline oxygen electrodes

The authors describe the identification and testing of electrocatalysts and supports for the positive electrode of moderate-temperature, single-unit, rechargeable alkaline fuel cells. Recent work on Na(x)Pt3O4, a potential bifunctional catalyst, is described, as well as the application of novel approaches to the development of more efficient bifunctional electrode structures. The three dual-character electrodes considered here showed similar superior performance; the Pt/RhO2 and Rh/RhO2 electrodes showed slightly better performance than the Pt/IrO2 electrode. It is concluded that Na(x)Pt3O4 continues to be a promising bifunctional oxygen electrode catalyst but requires further investigation and development.

Swette, L.↗

Chemisorption studies of Pt/SnO2 catalysts

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Brown, Kenneth G.↗

A First Attempt to Simulate the Natural Formation of Meteoritic Organics

Our working hypothesis in these experiments is that meteoritic organics are a mixture of materials made both in the interstellar medium and in the solar nebula that were further processed within meteorite parent bodies to produce what we see today. The material synthesized in the pre-solar environment is currently under study in several laboratories, though to our knowledge none are investigating the changes that might occur as the result of metamorphic processes on the parent body itself. Material made in the Solar Nebula results from a Fischer-Tropsch type (FTT) synthesis as CO and H2 react on grain surfaces to make methane, as well as more complex species. The products of these reactions using natural catalysts have been well-studied and a calculation of the potential efficiency of FTT reactions in the solar nebula demonstrates that they could contribute significantly to the composition of material near 3 AU.

Gardner, Kathryn↗

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Two cooperative phenomena are required the development of highly efficient porous electrocatalysts: (1) is an increase in the electrocatalytic activity of the catalyst particle; and (2) is the availability of that electrocatalyst particle for the electromechanical reaction. The two processes interact with each other so that improvements in the electrochemical activity must be coupled with improvements in the availability of the electrocatalyst for reaction. Cost effective and highly reactive electrocatalysts were developed. The utilization of the electrocatalyst particles in the porous electrode structures was analyzed. It is shown that a large percentage of the electrocatalyst in anode structures is not utilized. This low utilization translates directly into a noble metal cost penalty for the fuel cell.

Stonehart, P.↗

Series Bosch System Development

State-of-the-art (SOA) carbon dioxide (CO2) reduction technology for the International Space Station produces methane as a byproduct. This methane is subsequently vented overboard. The associated loss of hydrogen ultimately reduces the mass of oxygen that can be recovered from CO2 in a closed-loop life support system. As an alternative to SOA CO2 reduction technology, NASA is exploring a Series-Bosch system capable of reducing CO2 with hydrogen to form water and solid carbon. This results in 100% theoretical recovery of oxygen from metabolic CO2. In the past, Bosch-based technology did not trade favorably against SOA technology due to a high power demand, low reaction efficiencies, concerns with carbon containment, and large resupply requirements necessary to replace expended catalyst cartridges. An alternative approach to Bosch technology, labeled "Series-Bosch," employs a new system design with optimized multi-stage reactors and a membrane-based separation and recycle capability. Multi-physics modeling of the first stage reactor, along with chemical process modeling of the integrated system, has resulted in a design with potential to trade significantly better than previous Bosch technology. The modeling process and resulting system architecture selection are discussed.

Abney, Morgan B.↗

Preparation and Evaluation of Multi-Layer Anodes of Solid Oxide Fuel Cell

The development of an energy device with abundant energy generation, ultra-high specific power density, high stability and long life is critical for enabling longer missions and for reducing mission costs. Of all different types of fuel cells, the solid oxide fuel cells (SOFC) is a promising high temperature device that can generate electricity as a byproduct of a chemical reaction in a clean way and produce high quality heat that can be used for other purposes. For aerospace applications, a power-to-weight of (is) greater than 1.0 kW/kg is required. NASA has a patented fuel cell technology under development, capable of achieving the 1.0 kW/kg figure of merit. The first step toward achieving these goals is increasing anode durability. The catalyst plays an important role in the fuel cells for power generation, stability, efficiency and long life. Not only the anode composition, but its preparation and reduction are key to achieving better cell performance. In this research, multi-layer anodes were prepared varying the chemistry of each layer to optimize the performance of the cells. Microstructure analyses were done to the new anodes before and after fuel cell operation. The cells' durability and performance were evaluated in 200 hrs life tests in hydrogen at 850 C. The chemistry of the standard nickel anode was modified successfully reducing the anode degradation from 40% to 8.4% in 1000 hrs and retaining its microstructure.

Santiago, Diana↗

Origin of organic compounds on the primitive earth and in meteorites

The paper examines the role and relative contributions of different forms of energy to the synthesis of amino acids and other organic compounds on the primitive earth and in the solar nebula. Attention is directed mainly to the activation steps and formation of reactive intermediate compounds. Electric discharges appear to be not only the most efficient energy for amino acid synthesis but also yield a mixture of amino acids that is qualitatively and quantitatively the same as that found in the Murchison carbonaceous chondrite. Ultraviolet light is likely to have played a major role in prebiotic synthesis. The reaction of CO plus H2 plus NH3 on the surface of a Fischer-Tropsch catalyst produces reactive intermediates which lead to amino acids and other organic compounds in a much less efficient way than electric discharges.

Miller, S. L.↗