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At least 91 records · Page 5

Ruthenium Oxide Electrochemical Super Capacitor Optimization for Pulse Power Applications

Electrical actuator systems are being pursued as alternatives to hydraulic systems to reduce maintenance time, weight and costs while increasing reliability. Additionally, safety and environmental hazards associated with the hydraulic fluids can be eliminated. For most actuation systems, the actuation process is typically pulsed with high peak power requirements but with relatively modest average power levels. The power-time requirements for electrical actuators are characteristic of pulsed power technologies where the source can be sized for the average power levels while providing the capability to achieve the peak requirements. Among the options for the power source are battery systems, capacitor systems or battery-capacitor hybrid systems. Battery technologies are energy dense but deficient in power density; capacitor technologies are power dense but limited by energy density. The battery-capacitor hybrid system uses the battery to supply the average power and the capacitor to meet the peak demands. It has been demonstrated in previous work that the hybrid electrical power source can potentially provide a weight savings of approximately 59% over a battery-only source. Electrochemical capacitors have many properties that make them well-suited for electrical actuator applications. They have the highest demonstrated energy density for capacitive storage (up to 100 J/g), have power densities much greater than most battery technologies (greater than 30kW/kg), are capable of greater than one million charge-discharge cycles, can be charged at extremely high rates, and have non-explosive failure modes. Thus, electrochemical capacitors exhibit a combination of desirable battery and capacitor characteristics.

Merryman, Stephen A.↗

Supported transition metal catalysts for para- to ortho-hydrogen conversion

The main goal of this study was to develop and improve on existing catalysts for the conversion of ortho- to para-hydrogen. Starting with a commercially available Air Products nickel silicate, which had a beta value of 20, we were trying to synthesize catalysts that would be an improvement to AP. This was accomplished by preparing silicates with various metals as well as different preparation methods. We also prepared supported ruthenium catalysts by various techniques using several metal precursors to improve present technology. What was also found was that the activation conditions prior to catalytic testing was highly important for both the silicates and the supported ruthenium catalysts. While not the initial focus of the research, we made some interesting observations into the adsorption of H2 on ruthenium. This helped us to get a better understanding of how ortho- to para-H2 conversion takes place, and what features in a catalyst are important to optimize activity. Reactor design was the final area in which some interesting conclusions were drawn. As discussed earlier, the reactor catalyst bed must be constructed using straight 1/8 feet OD stainless steel tubing. It was determined that the use of 1/4 feet OD tubing caused two problems. First, the radius from the center of the bed to the wall was too great for thermal equilibrium. Since the reaction of ortho- to para-H2 is exothermic, the catalyst bed center was warmer than the edges. Second, the catalyst bed was too shallow using a 1/4 feet tube. This caused reactant blow-by which was thought to decrease the measured activity when the flow rate was increased. The 1/8 feet tube corrected both of these concerns.

Brooks, Christopher J.↗

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↗

Sol-Gel Process for Making Pt-Ru Fuel-Cell Catalysts

A sol-gel process has been developed as a superior alternative to a prior process for making platinum-ruthenium alloy catalysts for electro-oxidation of methanol in fuel cells. The starting materials in the prior process are chloride salts of platinum and ruthenium. The process involves multiple steps, is time-consuming, and yields a Pt-Ru product that has relatively low specific surface area and contains some chloride residue. Low specific surface area translates to incomplete utilization of the catalytic activity that might otherwise be available, while chloride residue further reduces catalytic activity ("poisons" the catalyst). In contrast, the sol-gel process involves fewer steps and less time, does not leave chloride residue, and yields a product of greater specific area and, hence, greater catalytic activity. In this sol-gel process (see figure), the starting materials are platinum(II) acetylacetonate [Pt(C5H7O2)2, also denoted Pt-acac] and ruthenium(III) acetylacetonate [Ru(C5H7O2)3, also denoted Ru-acac]. First, Pt-acac and Ru-acac are dissolved in acetone at the desired concentrations (typically, 0.00338 moles of each salt per 100 mL of acetone) at a temperature of 50 C. A solution of 25 percent tetramethylammonium hydroxide [(CH3)4NOH, also denoted TMAH] in methanol is added to the Pt-acac/Ruacac/ acetone solution to act as a high-molecular-weight hydrolyzing agent. The addition of the TMAH counteracts the undesired tendency of Pt-acac and Ru-acac to precipitate as separate phases during the subsequent evaporation of the solvent, thereby helping to yield a desired homogeneous amorphous gel. The solution is stirred for 10 minutes, then the solvent is evaporated until the solution becomes viscous, eventually transforming into a gel. The viscous gel is dried in air at a temperature of 170 C for about 10 hours. The dried gel is crushed to make a powder that is the immediate precursor of the final catalytic product. The precursor powder is converted to the final product in a controlled-atmosphere heat treatment. Desirably, the final product is a phase-pure (Pt phase only) Pt-Ru powder with a high specific surface area. The conditions of the controlled- atmosphere heat are critical for obtaining the aforementioned desired properties. A typical heat treatment that yields best results for a catalytic alloy of equimolar amounts of Pt and Ru consists of at least two cycles of heating to a temperature of 300 C and holding at 300 C for several hours, all carried out in an atmosphere of 1 percent O2 and 99 percent N2. The resulting powder consists of crystallites with typical linear dimensions of <10 nm. Tests have shown that the powder is highly effective in catalyzing the electro-oxidation of methanol.

Narayanan, Sekharipuram↗

Capture of volatile RuO 4 from oxidized simulated used nuclear fuel solutions

Ruthenium is a challenging fission product in used nuclear fuel (UNF) reprocessing due to its complex redox chemistry, variable speciation in nitric acid, partial extractability, and volatility. This work presents a strategy for Ru removal based on the volatilization of RuO 4 using the strong oxidant sodium bismuthate, followed by RuO 2 deposition onto various substrates. Among the materials tested, polymer-based substrates such as polyolefin wax film (Parafilm®), exhibited superior performance, achieving up to near-quantitative Ru removal from solution. After dissolution of the substrate, 99.6% of the Ru was recovered as RuO 2 . The deposition mechanism onto the polyolefin wax film involves both physisorption and chemical reaction through oxidative cleavage of olefinic bonds within the polymer. In contrast, on inorganic substrates such as Al foil, RuO 4 undergoes incomplete surface adsorption and reduction, as confirmed by FTIR and XPS analyses. This approach remains effective under conditions of simulated oxidation of UNF solutions, selectively removing Ru while leaving other fission products in solution. As a result, capture of RuO 4 offers a practical and efficient strategy for ruthenium decontamination and recovery, offering a route for integration into existing UNF reprocessing flowsheets to enhance overall process safety and performance.

Ruthenium↗

Phase Transformation and Water Adsorption Behavior of As‐Deposited and Annealed Ru Metal Thin Films Prepared by Atomic Layer Deposition

ABSTRACT Surfaces play a central role in catalytic processes, and understanding the transformation of ruthenium metal into ruthenium oxide during annealing is essential for tailoring functional catalytic interfaces. In this study, we systematically investigate ≈22 nm thick Ru metal films deposited by atomic layer deposition (ALD) at 300°C, focusing on their chemical composition, structural evolution, and surface hydration behavior following post‐deposition annealing in air from 400 to 600°C. Lab‐based and synchrotron X‐ray photoelectron spectroscopy (XPS) reveal a gradual conversion from metallic Ru to fully oxidized Ru 4+ with increasing annealing temperature, accompanied by a corresponding increase in lattice oxygen. X‐ray diffraction (XRD) shows amorphous Ru oxide phases at 400°C and 500°C that evolve into crystalline RuO 2 at 600°C, while atomic force microscopy (AFM) indicates enhanced grain growth and surface roughening upon annealing. Ambient‐pressure XPS (AP‐XPS) under controlled H 2 O vapor environments (1–17 Torr) demonstrates that samples annealed at 400°C and 500°C exhibit initially high hydroxyl coverage that decreases with increasing water vapor pressure, concurrent with a rise in molecular H 2 O adsorption. In contrast, the crystalline RuO 2 surface formed at 600°C maintains stable hydroxylation and supports increased water uptake. Overall, this work provides fundamental insight into Ru oxide–H 2 O interactions and establishes design principles for engineering oxide surfaces optimized for electrocatalytic applications.

APXPS↗

Promoted Ru/PrOx Catalysts for Mild Ammonia Synthesis

Ammonia synthesis is one of the most important chemical reactions. Due to thermodynamic restrictions and the reaction requirements of the current commercial iron catalysts, it is also one of the worst reactions for carbon dioxide emissions and energy usage. Ruthenium-based catalysts can substantially improve the environmental impact as they operate at lower pressures and temperatures. In this work, we provide a screening of more than 40 metals as possible promoter options based on a Ru/Pr2O3 catalyst. Cesium was the best alkali promoter and was held constant for the series of double-promoted catalysts. Ten formulations outperformed the Ru-Cs/PrOx benchmark, with barium being the best second promoter studied and the most cost-effective option. Designs of experiments were utilized to optimize both the pretreatment conditions and the promoter weight loadings of the doubly promoted catalyst. As a result, optimization led to a more than five-fold increase in activity compared to the unpromoted catalyst, therefore creating the possibility for low-ruthenium ammonia synthesis catalysts to be used at scale. Further, we have explored the roles of promoters using kinetic analysis, X-ray Photoelectron Spectroscopy (XPS), and in situ infrared spectroscopy. Here, we have shown that the role of barium is to act as a hydrogen scavenger and donor, which may permit new active sites for the catalyst, and have demonstrated that the associative reaction mechanism is likely used for the unpromoted Ru/PrOx catalyst with hydrogenation of the triple bond of the dinitrogen occurring before any dinitrogen bond breakage.

Chemistry↗

Regeneration of Benzimidazole-Based Organohydrides Mediated by Ru Catalysts

Benzimidazole-based organohydrides (BIHs) are versatile hydride, electron, and proton donors in a variety of artificial photosynthetic systems for the generation of solar fuels. Currently, BIHs are often used in stoichiometric rather than catalytic processes. The catalytic regeneration of BIHs from their oxidized form (BI + ) is an urgent necessity in order to allow the development of recyclable systems and devices, but viable examples are scarce and require large overpotentials. Here, in this study, we report the electrocatalytic regeneration of a series of BIHs with varying hydricities, promoted by a ruthenium half-sandwich complex, [(HMB)Ru(bpy)(H)]+ (HMB = η 6 -C 6 Me 6 , bpy = 2,2′-bipyridine), in the presence of tributylammonium (HNBu 3 + ) as a proton source. This metal hydride was generated in situ from the 2e - reduction/protonation of the corresponding solvento-complex. In comparison to the direct cathodic reduction of BI + in the presence of HNBu 3 + , the use of this ruthenium catalyst allowed efficient regeneration of BIHs at less negative potentials, with Faradaic efficiencies up to 80% and significantly higher conversion yields due to the circumvention of the dimerization pathway and the stepwise reduction and protonation reactions. Finally, the thermodynamic challenges involved in the regeneration of very hydridic BIHs mediated by Ru hydride catalysts were examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ammonia Decomposition Catalyst Development for Palladium Membrane Reactor

Conclusions and Questions • Tritiated ammonia is a persistent problem in tritium operations. • Tritiated ammonia can be completely converted to nitrogen and tritium using a permeation membrane reactor. • Ruthenium trimetallic catalysts are highly active at PdAg temperatures. • Catalysts from nitrate precursors are more active than from chloride. • Nickel-based catalysts are potential replacements for ruthenium catalysts.

Guin, Tyler [Savannah River National Laboratory (S↗

The catalytic removal of ammonia and nitrogen oxides from spacecabin atmospheres

Investigations were made on methods for the removal of ammonia and to a lesser extent nitrogen oxides in low concentrations from air. The catalytic oxidation of ammonia was studied over a temperature range of 250 F to 600 F and a concentration range 20 ppm to 500 ppm. Of the catalysts studied, 0.5 percent ruthenium supported on alumina was found to be superior. This material is active at temperatures as low as 250 F and was found to produce much less nitrous oxide than the other two active catalysts, platinum on alumina and Hopcalite. A quantitative design model was developed which will permit the performance of an oxidizer to be calculated. The ruthenium was found to be relatively insensitive to low concentrations of water and to oxygen concentration between 21 percent and 100 percent. Hydrogen sulfide was found to be a poison when injected in relatively large quantities. The adsorption of ammonia by copper sulfate treated silica gel was investigated at temperatures of 72 F and 100 F. A quantitative model was developed for predicting adsorption bed behavior.

Gully, A. J.↗

Catalytic oxidation of waste materials

Aqueous stream of human waste is mixed with soluble ruthenium salts and is introduced into reactor at temperature where ruthenium black catalyst forms on internal surfaces of reactor. This provides catalytically active surface to convert oxidizable wastes into breakdown products such as water and carbon dioxide.

Jagow, R. B.↗

Process of forming catalytic surfaces for wet oxidation reactions

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Jagow, R. B.↗

Sensing strategies for toxic vapor detection

This work was motivated by the recommendations of the American Conference of Governmental Industrial Hygienists (ACGIH) that threshold limits for hydrazine, H2N-NH2 in air be lowered from 100 to 10 parts-per-billion (ppb) concentration levels. Hydrazine is one of the high-energy propellants used in large volumes in Space Shuttle, Titan, payloads, and other aerospace operations. Since analytical methods presently available for hydrazine detection and/or determination do not satisfy such low levels of detection, the ultimate goal of this research is the development and characterization of a portable and compact chemical sensor ideally capable to detect (in real time) 1 ppb of hydrazine, continuously and reversibly. The laboratory prototype developed as part of this project is comprised of: (1) a reactor part in which H2N-NH2 reacts, generating chemiluminescence emission, with tris(2,2'-bipyridine)ruthenium(III), which is immobilized on an ion-exchange polymeric materials of a perfluorinated hydrocarbon containing sulfonate groups as exchange centers (Nafion); (2) an electrochemical three-electrode cell posed at a potential at which the immobilized ruthenium complex could be reoxidized to the 3-oxidation state (as to provide reversible and continuous detection); and (3) a low power consumption photomultiplier tube to collect and quantitatively integrate the emitted photons with the help of auxiliary electronics and readout device.

Mottola, Horacio A.↗

Joint Development of a Fourth Generation Single Crystal Superalloy

A new, fourth generation, single crystal superalloy has been jointly developed by GE Aircraft Engines, Pratt & Whitney, and NASA. The focus of the effort was to develop a turbine airfoil alloy with long-term durability for use in the High Speed Civil Transport. In order to achieve adequate long-time strength improvements at moderate temperatures and retain good microstructural stability, it was necessary to make significant composition changes from 2nd and 3rd generation single crystal superalloys. These included lower chromium levels, higher cobalt and rhenium levels and the inclusion of a new alloying element, ruthenium. It was found that higher Co levels were beneficial to reducing both TCP precipitation and SRZ formation. Ruthenium caused the refractory elements to partition more strongly to the ' phase, which resulted in better overall alloy stability. The final alloy, EPM 102, had significant creep rupture and fatigue improvements over the baseline production alloys and had acceptable microstructural stability. The alloy is currently being engine tested and evaluated for advanced engine applications.

Walston, S.↗

Oxidation-reduction catalyst and its process of use

This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

Jordan, Jeffrey D.↗