Asymmetric hydrogenation using modified cellulose-palladium catalysts
Cellulose ion exchanger palladium catalysts preparation and applications in asymmetric hydrogenation reactions
Harada, K.↗
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Asymmetric hydrogenation using modified ion exchange resin-palladium catalysts
Benzoylformic and alpha-acetamidoacrylic acid hydrogenation, using modified ion exchange resin- palladium catalysts
Harada, K.↗
Observations of exoelectron emission associated with heterogeneous catalysis
It is suggested that the exoelectron emission from the catalyst may be used to monitor the rate of oxidation of CO and CH4 over palladium catalysts. Indirect heating of the catalyst and atmospheric pressure have no effect upon this monitoring system. Although the mechanism relating catalysis to exoelectron emission is not clear, it is considered possible that electron emission is triggered by the adsorption-desorption cycle.
Hoenig, S. A.↗
Chemical Characterization and Thermal Stressing Studies of Perfluorohexane Fluids for Space-Based Applications
Perfluorohexane (PFH), C6F14, is a perfluorocarbon fluid. Several PFH fluids with different isomer concentrations were evaluated for use in an upcoming NASA space experiment. Samples tested included two commercially obtained high-purity n-perfluorohexane (n-PFH) fluids and a technical grade mixture of C6F14 branched and linear isomers (FC-72(TradeMark)). These fluids were evaluated for exact chemical composition, impurity purity and high temperature degradation behavior (pyrolysis). Our investigation involved simulated thermal stressing studies of PFH fluids under conditions likely to occur in the event of an atmospheric breach within the International Space Station (ISS) and subsequent exposure of the vapors to the high temperature and catalyst present in its Trace Contaminant Control Subsystem (TCCS). Exposure to temperatures in the temperature range of 200-450 C in an inert or oxidizing atmosphere, with and without the presence of catalyst was investigated. The most aggressive conditions studied were exposure of PFH vapors to 450 C in air and in the presence of TCCS (palladium) catalyst. Gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC) analyses were conducted on the perfluorohexane samples before and after pyrolysis. The FC-72 and n-PFH samples showed no significant degradation following pyrolysis even under the most aggressive study conditions. Some trace level impurities associated with the PFH samples such as linear perfluorocarbon monohydrides or monoiodides were destroyed by pyrolysis at the upper limit. Other trace level impurities such as olefinic or cycloolefinic perfluorocarbons were converted into oxidation products by pyrolysis. The purity of PFH following pyrolysis actually increased slightly as a consequence since these trace contaminants were effectively scrubbed from the samples. However, since the initial concentrations of the thermally-impacted impurities were so low, the net effect was trivial. A potential byproduct of exposure of perfluorohexane fluids to high temperatures is the production of perfluoroisobutene (PFiB), which is extremely toxic. An ultra-high sensitivity PFiB-specific analysis based on GC-MS with negative ion chemical ionization (NICI) detection was used to evaluate the samples following thermal stressing. The perfluorohexanes examined here under conditions reflective of the ISS TCCS environment showed no signs of PFiB production with an analytical detection limit of 10 part per billion (ppb v/v).
Arnold, William A.↗
Design and fabrication of a trace contaminant removal system for Apollo, phase III Final report, Sep. 1965 - Feb. 1966
Sorbent material and platinum and palladium catalyst testing for development of Apollo spacecraft trace contaminant removal system
APOLLO SPACECRAFT↗
Hydrogen-oxygen powered internal combustion engine
Hydrogen at 300 psi and oxygen at 800 psi are injected sequentially into the combustion chamber to form hydrogen-rich mixture. This mode of injection eliminates difficulties of preignition, detonation, etc., encountered with carburated, spark-ignited, hydrogen-air mixtures. Ignition at startup is by means of a palladium catalyst.
Cameron, H.↗
Hydrogen eliminator
Vented hydrogen is converted into water by mixing hydrogen with sufficient air to ensure that a flame cannot be maintained and then passing it through a reactor containing palladium catalyst; reaction takes place at relatively low temperature. Device may have wide range of applications for air purification.
Kiraly, R. J.↗
A Process for Preparing 1,3-Diamino-5-Pentafluorosulfanylbenzene and Polymers Therefrom
Diamines have shown their utility in the formation of many polymers. Examples of these polymers include polyimides, polyamides, and epoxies. The properties of these polymers are often dependent on the diamine which is used to make the polymer. By the present invention, a process was developed to make a diamine containing pentafluorosulfanylbenzene moiety. This process involves two steps: the preparation of a dinitro precursor and the reduction of the dinitro compound to form the diamine. This diamine was then reacted with various dianhydrides, diacidchlorides, and epoxy resins to yield the corresponding polyimide, polyamide, and epoxy polymers. These polymers were then used to make films, a wire coating enamel, and a semi-permeable membrane. The novelty of this invention resides in the process to make the diamine. Traditionally, dinitro compounds are reduced with hydrazine or a catalyst such as palladium on charcoal. The catalyst which is used in this invention is platinum oxide. When this catalyst is used, it makes it possible to form a polymer-grade diamine.
St.clair, Anne K.↗
Stabilizing Semiconductor Devices With Hydrogen
Damage by radiation healed rapidly. Feature provides continuous, rapid recovery of devices from degradation caused by hot electrons, photons, and ionizing radiation. Several candidate sites for palladium film catalysts, inserted during manufacture as integral parts of devices. Paladium films made by evaporation, sputtering, or chemical-vapor deposition. If additional storage required, thick layer of palladium plated on inside of package surrounding device. Hydrogen stored by exposing palladium to hydrogen gas just before package sealed hermetically.
Overhauser, Albert W.↗
Making A Noble-Metal-On-Metal-Oxide Catalyst
Catalyst exhibits superior performance in oxidation of CO in CO2 lasers. Two-step process developed for preparing platinum- or palladium-on-tin-oxide catalyst for recombination of CO and O2, decomposition products that occur in high-voltage discharge region of closed-cycle CO2 laser. Process also applicable to other noble-metal/metal-oxide combinations.
Miller, Irvin M.↗
Impregnation of Catalytic Metals in Single-Walled Carbon Nanotubes for Toxic Gas Conversion in Life Support System
Carbon nanotubes (CNTs) possess extraordinary properties such as high surface area, ordered chemical structure that allows functionalization, larger pore volume, and very narrow pore size distribution that have attracted considerable research attention from around the world since their discovery in 1991. The development and characterization of an original and innovative approach for the control and elimination of gaseous toxins using single walled carbon nanotubes (SWNTs) promise superior performance over conventional approaches due to the ability to direct the selective uptake of gaseous species based on their controlled pore size, increased adsorptive capacity due to their increased surface area and the effectiveness of carbon nanotubes as catalyst supports for gaseous conversion. We present our recent investigation of using SWNTs as catalytic supporting materials to impregnate metals, such as rhodium (Rh), palladium (Pd) and other catalysts. A protocol has been developed to oxidize the SWNTs first and then impregnate the Rh in aqueous rhodium chloride solution, according to unique surface properties of SWNTs. The Rh has been successfully impregnated in SWNTs. The Rh-SWNTs have been characterized by various techniques, such as TGA, XPS, TEM, and FTIR. The project is funded by a NASA Research Announcement Grant to find applications of single walled nanocarbons in eliminating toxic gas Contaminant in life support system. This knowledge will be utilized in the development of a prototype SWNT KO, gas purification system that would represent a significant step in the development of high efficiency systems capable of selectively removing specific gaseous for use in regenerative life support system for human exploration missions.
Li, Jing↗
Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers
Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.
Schryer, David R.↗
Inorganic ion exchange membrane fuel cell quarterly progress report, period ending 10 apr. 1965
Inorganic ion exchange membrane for improving mass and heat transfer of fuel cells using palladium and platinum black as catalyst
HEAT TRANSFER↗
Review of Laser Ablation Process for Single Wall Carbon Nanotube Production
Different types of lasers are now routinely used to prepare single wall carbon nanotubes (SWCNTs). The original method developed by researchers at Rice University utilized a "double pulse laser oven" process. A graphite target containing about 1 atomic percent of metal catalysts is ablated inside a 1473K oven using laser pulses (10 ns pulse width) in slow flowing argon. Two YAG lasers with a green pulse (532 nm) followed by an IR pulse (1064 nm) with a 50 ns delay are used for ablation. This set up produced single wall carbon nanotube material with about 70% purity having a diameter distribution peaked around 1.4 nm. The impurities consist of fullerenes, metal catalyst clusters (10 to 100 nm diameter) and amorphous carbon. The rate of production with the initial set up was about 60 mg per hour with 10Hz laser systems. Several researchers have used variations of the lasers to improve the rate, consistency and study effects of different process parameters on the quality and quantity of SWCNTs. These variations include one to three YAG laser systems (Green, Green and IR), different pulse widths (nano to microseconds as well as continuous) and different laser wavelengths (Alexandrite, CO, CO2, free electron lasers in the near to far infrared). It is noted that yield from the single laser (Green or IR) systems is only a fraction of the two laser systems. The yield seemed to scale up with the repetition rate of the laser systems (10 to 60 Hz) and depended on the beam uniformity and quality of the laser pulses. The shift to longer wavelength lasers (free electron, CO and CO2) did not improve the quality, but increased the rate of production because these lasers are either continuous (CW) or high repetition rate pulses (kHz to MHz). The average power and the peak power of the lasers seem to influence the yields. Very high peak powers (MegaWatts per square centimeter) are noted to increase ablation of bigger particles with reduced yields of SWCNTs. Increased average powers seem to help the conversion of the carbon from target into vapor phase to improve formation of nanotubes. The use of CW far infrared lasers reduced the need for the oven, at the expense of controlled ablation. Some of these variations are tried with different combinations and concentrations of metal catalysts (Nickel with Cobalt, Iron, Palladium and Platinum) different buffer gases (e.g. Helium); with different oven temperatures (Room temperature to 1473K); under different flow conditions (1 to 1000 kPa) and even different porosities of the graphite targets. It is to be noted that the original Cobalt and Nickel combination worked best, possibly because of improved carbonization with stable crystalline phases. The mean diameter and yield seemed to increase with increasing oven temperatures. Thermal conductivity of the buffer gas and flow conditions dictate the quality as well as quantity of the SWCNTs. Faster flows, lower pressures and heavier gases seem to increase the yields. This review will attempt to cover all these variations and their relative merits. Possible growth mechanisms under these different conditions will also be discussed.
Arepalli, Sivaram↗
Degradation of TATP, TNT, and RDX using mechanically alloyed metals
Bimetallic alloys prepared in a ball milling process, such as iron nickel (FeNi), iron palladium (FePd), and magnesium palladium (MgPd) provide in situ catalyst system for remediating and degrading nitro explosive compounds. Specifically, munitions, such as, 2,4,6-trinitrotoluene (TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), nitrocellulose and nitroglycerine that have become contaminants in groundwater, soil, and other structures are treated on site to remediate explosive contamination.
Clausen, Christian↗
Investigation of low temperature carbon monoxide oxidation catalysts
Carbon monoxide generation rates related to the use of commerical equipment in Spacelab, added to the normal metabolic and subsystem loads, will produce carbon monoxide levels in excess of the maximum allowable concentration. In connection with the sensitivity of carbon monoxide oxidation catalysts to poisoning at room temperature, catalysts for an oxidation of carbon monoxide at low temperatures have been investigated. It was found that platinum and palladium are the only effective room temperature catalysts which are effective at 333 K. Hopcalite was ineffective at ambient temperatures, but converted CO with 100 percent efficiency at 333 K. Poisoning tests showed the noble metal catalysts to be very sensitive, and Hopcalite to be very resistant to poisoning.
Jagow, R. B.↗
Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use
Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.
Quinn, Jacqueline↗
Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration
The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.
Udom, I.↗