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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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Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate

Hydrazine is an important industrial chemical and fuel that has attracted considerable attention for use in liquid fuel cells. Ideally, hydrazine could be prepared via direct oxidative coupling of ammonia, but thermodynamic and kinetic factors limit the viability of this approach. Here, the present study evaluates three different electrochemical strategies for the oxidative homocoupling of benzophenone imine, a readily accessible ammonia surrogate. Hydrolysis of the resulting benzophenone azine affords hydrazine and benzophenone, with the latter amenable to recycling. The three different electrochemical N–N coupling methods are (1) a proton-coupled electron-transfer process promoted by a phosphate base, (2) an iodine-mediated reaction involving intermediate N–I bond formation, and (3) a copper-catalyzed N–N coupling process. Analysis of the thermodynamic efficiencies for these electrochemical imine-to-azine oxidation reactions reveals low overpotentials (η) for the copper- and iodine-mediated processes (390 and 470 mV, respectively), but a much higher value for the proton-coupled pathway (η ≈ 1.6 V). A similar approach is used to assess molecular electrocatalytic methods for electrochemical oxidation of ammonia to dinitrogen.

25 ENERGY STORAGE↗

Understanding Nitrogen Fixation

The purpose of our program is to explore fundamental chemistry relevant to the discovery of energy efficient methods for the conversion of atmospheric nitrogen (N 2 ) into more value-added nitrogen-containing organic molecules. Such transformations are key for domestic energy security and the reduction of fossil fuel dependencies. With DOE support, we have synthesized families of zirconium and hafnium dinitrogen complexes with elongated and activated N-N bonds that exhibit rich N 2 functionalization chemistry. Having elucidated new methods for N-H bond formation from dihydrogen, C-H bonds and Broensted acids, we have since turned our attention to N-C bond construction. These reactions are particularly important for the synthesis of amines, heterocycles and hydrazines with a range of applications in the fine and commodity chemicals industries and as fuels. One recent highlight was the discovery of a new N 2 cleavage reaction upon addition of carbon monoxide which resulted in the synthesis of an important fertilizer, oxamide, from the diatomics with the two strongest bonds in chemistry.

03 NATURAL GAS↗

Fuel cell sesquicentennial

The development of fuel cell technology is summarized, and the potential for utility-type fuel cell installations is assessed on the occasion of the 150th anniversary of the construction of the first fuel cell by Sir William Grove. The only functional fuel-cell systems developed to date, the hydrogen-oxygen cells used by NASA, are indicated, and hydrazine and alcohol (methanol) cells are considered. Areas requiring development before the implementation of fuel cells as general purpose utility-type electric generators include catalysts for naturally occurring hydrocarbons or processes for low-cost methanol or hydrazine production, efficient means of scrubbing and enriching air, self-regulating systems, and 15- to 20-fold power density increases. It is argued that although ideas for eliminating certain of the above-mentioned problems have been proposed, fuel-cell systems can never be expected to equal the efficiency, reliability and low cost of conventional power plants, and thus developmental support should be discontinued.

Cohn, E. M.↗

Impact of Advances in Anion Exchange Membranes and Ionomers on Alkaline Fuel Cells

Abstract The operation of low‐temperature electrochemical energy conversion systems (fuel cells, electrolyzers) at high pH values is of perennial interest due to the possibility of moving away from expensive platinum group metal catalysts and reducing cost. Historically, the anion exchange membranes (AEMs) and ionomers have been hampered by performance (ionic conductivity, mechanical strength) and chemical stability issues. In this context, select developments over the past decade in alternate AEM chemistries, water management methods, and production of membrane electrode assemblies (MEAs) that have enabled a significant leap in performance of alkaline fuel cells are examined. These developments are linked to performance improvements in alkaline H 2 /O 2 fuel cells and also consider developments in alkaline fuel cells using nitrogen‐containing fuels (ammonia, hydrazine), carbon‐containing fuels (alcohols, glycols), and boron‐containing fuels (sodium borohydride, ammonia borane). Finally, current challenges and bottlenecks are identified, and potential solutions are proposed.

Chemistry↗

Fuel-Cell Power Source Based on Onboard Rocket Propellants

The use of onboard rocket propellants (dense liquids at room temperature) in place of conventional cryogenic fuel-cell reactants (hydrogen and oxygen) eliminates the mass penalties associated with cryocooling and boil-off. The high energy content and density of the rocket propellants will also require no additional chemical processing. For a 30-day mission on the Moon that requires a continuous 100 watts of power, the reactant mass and volume would be reduced by 15 and 50 percent, respectively, even without accounting for boiloff losses. The savings increase further with increasing transit times. A high-temperature, solid oxide, electrolyte-based fuel-cell configuration, that can rapidly combine rocket propellants - both monopropellant system with hydrazine and bi-propellant systems such as monomethyl hydrazine/ unsymmetrical dimethyl hydrazine (MMH/UDMH) and nitrogen tetroxide (NTO) to produce electrical energy - overcomes the severe drawbacks of earlier attempts in 1963-1967 of using fuel reforming and aqueous media. The electrical energy available from such a fuel cell operating at 60-percent efficiency is estimated to be 1,500 Wh/kg of reactants. The proposed use of zirconia-based oxide electrolyte at 800-1,000 C will permit continuous operation, very high power densities, and substantially increased efficiency of conversion over any of the earlier attempts. The solid oxide fuel cell is also tolerant to a wide range of environmental temperatures. Such a system is built for easy refueling for exploration missions and for the ability to turn on after several years of transit. Specific examples of future missions are in-situ landers on Europa and Titan that will face extreme radiation and temperature environments, flyby missions to Saturn, and landed missions on the Moon with 14 day/night cycles.

Ganapathi, Gani↗

Permeation Resistance of Chlorinated Polyethylene Against Hydrazine Fuels

The permeation resistance of chlorinated polyethylene (CPE) used in chemical protective clothing against the aerospace fuels hydrazine, monomethylhydrazine (MMH), and uns-dimethylhydrazine (UDMH) was determined by measuring breakthrough times and time-averaged vapor transmission rates using an ASTM F 739 permeation cell. Two exposure scenarios were simulated: a 2 hour (h) fuel vapor exposure, and a liquid fuel "splash" followed by a 2 h vapor exposure. To simulate internal suit pressure during operation, a positive differential pressure of 0.3 in. water (75 Pa) on the collection side of the permeation apparatus was used. Breakthrough was observed after exposure to liquid MMH, and to vapor and liquid UDMH. No breakthrough was observed after exposure to vapor and liquid hydrazine, or vapor MMH. A model was then used to calculate propellant concentrations inside a totally encapsulating chemical protective suit based on the ASTM permeation data obtained in the present study. Concentrations were calculated under conditions of fixed vapor transmission rate, variable breathing air flow rate, and variable splash exposure area. Calculations showed that the maximum allowable permeation rates of hydrazine fuels through CPE were of the order of 0.05 to 0.08 ng sq cm/min for encapsulating suits with low breathing air flow rates (of the order of 5 scfm or 140 L/min). Above these permeation rates, the 10 parts per billion (ppb) threshold limit value time - weighted average could be exceeded for chemical protective suits having a CPE torso. To evaluate suit performance at ppb level concentrations, use of a sensitive analytical method such as cation exchange high performance liquid chromatography with amperometric detection was found to be essential.

Waller, J. M.↗

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

36 MATERIALS SCIENCE↗

Hydrazine monopropellant reciprocating engine development

A hydrazine fueled piston engine for providing 11.2 kW was developed to satisfy the need for an efficient power supply in the range from 3.7 to 74.6 kW where existing nonair-breathing power supplies such as fuel cells or turbines are inappropriate. The engine was developed for an aircraft to fly to 21.3 km and above and cruise for extended periods. A remotely piloted aircraft and the associated flight control techniques for this application were designed. The engine is geared down internally (2:1) to accommodate a 1.8 m diameter propeller. An alternator is included to provide electrical power. The pusher-type engine is mounted onto the aft closure of the fuel tank, which also provides mounting for all other propulsion equipment. About 20 hrs of run time demonstrated good efficiency and adequate life. One flight test to 6.1 km was made using the engine with a small fixed-pitch four-bladed propeller. The test was successful in demonstrating operational characteristics and future potential.

Akkerman, J. W.↗

Hydrazine monopropellant reciprocating engine development

A hydrazine-fueled piston-type engine for providing 11.2 kW (15 hp) has been developed to satisfy the need for an efficient power supply in the range from 3.7 to 74.6 kW (5 to 100 hp) where existing nonair-breathing power supplies such as fuel cells or turbines are inappropriate. The engine was developed for an aircraft to fly to 21.3 km (70,000 ft) and above and cruise for extended periods. The NASA Hugh L. Dryden Flight Research Center developed a remotely piloted aircraft and the associated flight control techniques for this application. About 20 hr of run time have demonstrated good efficiency and adequate life. One flight test to 6.1 km (20,000 ft) has been made using the engine with a small fixed-pitch four-bladed propeller. The test was successful in demonstrating operational characteristics and future potential.

Akkerman, J. W.↗

Space Shuttle Upgrades Advanced Hydraulic Power System

Three Auxiliary Power Units (APU) on the Space Shuttle Orbiter each provide 145 hp shaft power to a hydraulic pump which outputs 3000 psi hydraulic fluid to 41 hydraulic actuators. A hydrazine fuel powered APU utilized throughout the Shuttle program has undergone many improvements, but concerns remain with flight safety, operational cost, critical failure modes, and hydrazine related hazards. The advanced hydraulic power system (AHPS), also known as the electric APU, is being evaluated as an upgrade to replace the hydrazine APU. The AHPS replaces the high-speed turbine and hydrazine fuel supply system with a battery power supply and electric motor/pump that converts 300 volt electrical power to 3000 psi hydraulic power. AHPS upgrade benefits include elimination of toxic hydrazine propellant to improve flight safety, reduction in hazardous ground processing operations, and improved reliability. Development of this upgrade provides many interesting challenges and includes development of four hardware elements that comprise the AHPS system: Battery - The battery provides a high voltage supply of power using lithium ion cells. This is a large battery that must provide 28 kilowatt hours of energy over 99 minutes of operation at 300 volts with a peak power of 130 kilowatts for three seconds. High Voltage Power Distribution and Control (PD&C) - The PD&C distributes electric power from the battery to the EHDU. This 300 volt system includes wiring and components necessary to distribute power and provide fault current protection. Electro-Hydraulic Drive Unit (EHDU) - The EHDU converts electric input power to hydraulic output power. The EHDU must provide over 90 kilowatts of stable, output hydraulic power at 3000 psi with high efficiency and rapid response time. Cooling System - The cooling system provides thermal control of the Orbiter hydraulic fluid and EHDU electronic components. Symposium presentation will provide an overview of the AHPS upgrade, descriptions of the four hardware elements, and a summary of development results to date.

Source record↗

Homogeneous electrocatalytic oxidation of ammonia to N 2 under mild conditions

We report that ruthenium polypyridyl complexes can catalyze ammonia oxidation to dinitrogen at room temperature and ambient pressure. During bulk electrolysis experiments, gas chromatography and mass spectrometry analysis of the headspace in the electrochemical cell showed that dinitrogen and dihydrogen are generated from ammonia with high faradaic efficiencies. A proposed mechanism where a hydrazine complex is the initial N–N bonded intermediate is supported by chemical and electrochemical experiments. This is a well-defined system for homogeneous electrocatalytic ammonia oxidation. This work establishes a platform for answering mechanistic questions relevant to using ammonia to store and distribute renewable energy.

08 HYDROGEN↗

Putting chromium on the map for N 2 reduction: production of hydrazine and ammonia. A study of cis -M(N 2 ) 2 (M = Cr, Mo, W) bis(diphosphine) complexes

The first complete structurally and spectroscopically characterized series of isostructural Group 6 N 2 complexes is reported in this paper. Protonolysis experiments on cis-[M(N 2 ) 2 (P Et N R P Et ) 2 ] (M = Cr, Mo, W; R = 2,6-difluorobenzyl) reveal that only Cr affords N 2 H 5 + and NH 4 + from the reduction of the N 2 ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗