Asymmetric hydrogenation using modified cellulose-palladium catalysts
Cellulose ion exchanger palladium catalysts preparation and applications in asymmetric hydrogenation reactions
Harada, K.↗
SEARCH · Engineering Papers
Results for “Palladium”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Effect of hydrogen on tensile properties of palladium-hydrogen system
Hydrogen absorption effects on tensile properties of palladium wire
Otterson, D. A.↗
Asymmetric hydrogenation using modified ion exchange resin-palladium catalysts
Benzoylformic and alpha-acetamidoacrylic acid hydrogenation, using modified ion exchange resin- palladium catalysts
Harada, K.↗
The effect of hydrogen on the tensile properties of palladium
Hydrogen content effect on annealed and work hardened palladium wire tensile properties, determining yield/tensile stress and elongation
Otterson, D. A.↗
Levitation calorimetry. IV - The thermodynamic properties of liquid cobalt and palladium.
Some of the thermodynamic properties of liquid cobalt and palladium investigated by means of levitation calorimetry are reported and discussed. The presented data include the specific heats and heats of fusion of the liquid metals, and the emissivities of the liquid metal surfaces.
Treverton, J. A.↗
Study of the kinetics of catalytic decomposition of hydrazine vapors on palladium
The decomposition rates of N2H4 on a palladium surface are studied. Experiments were conducted in a circulating unit at atmosphere pressure. The experimental method is described. The laws found for the reaction kinetics are explained by equations.
Khomenko, A. A.↗
Palladium-chromium static strain gages for high temperatures
An electrical resistance strain gage that can provide accurate static strain measurement to a temperature of 1500 F or above is being developed both in fine wire and thin film forms. The gage is designed to be temperature compensated on any substrate material. It has a dual element: the gage element is a special alloy, palladium-13wt percent chromium (PdCr), and the compensator element is platinum (Pt). Earlier results of a PdCr based wire gage indicated that the apparent strain of this gage can be minimized and the repeatability of the apparent strain can be improved by prestabilizing the gage on the substrate for a long period of time. However, this kind of prestabilization is not practical in many applications and therefore the development of a wire gage which is prestabilized before installation on the substrate is desirable. This paper will present our recent progress in the development of a prestabilized wire gage which can provide meaningful strain data for the first thermal cycle. A weldable PdCr gage is also being developed for field testing where conventional flame-spraying installation can not be applied. This weldable gage is narrower than a previously reported gage, thereby allowing the gage to be more resistant to buckling under compressive loads. Some preliminary results of a prestabilized wire gage flame-sprayed directly on IN100, an engine material, and a weldable gage spot-welded on IN100 and SCS-6/(beta)21-S Titanium Matrix Composite (TMC), a National Aero-Space Plane (NASP) structure material, will be reported. Progress on the development of a weldable thin film gage will also be addressed. The measurement technique and procedures and the lead wire effect will be discussed.
Lei, Jih-Fen↗
A Miniature Palladium-Iron Thermometer for Temperatures Down to 0.05 K
Magnetic thermometers are appealing at temperatures below about 0.1 Kelvin, because the avoid the noise self-heating problems associated with resistive thermometers. In practical, metallic dilute electronic thermometers add the advantages of chemical stability, high thermal conductivity, and easy in heat sinking work we describe a palladium-iron thermometer which was designed to be small and conveniently packaged and optimized for use at temperatures down to 0.05 Kelvin. The device showed Curie-Weiss behavior above about 0.06 Kelvin, and we achieve 41 nK/ square root of z temperature resolution at a temperature of 49 mK. We describe the design and operation of this thermometers and present the test results.
Tuttle, Jim↗
Raman and FTIR Studies of Silicon Carbide Surface Damage from Palladium Implantation in Presence of Hydrogen
The ion implantation in a crystal such as silicon carbide will cause both damage in the ion track and in the substrate at the end of the ion track. We used both keV, and MeV Pd ions in fabricating electronic chemical sensors in silicon carbide, which can operate at elevated temperatures. In order to study the feasibility of fabricating an optical chemical sensor (litmus sensor), we need to understand the optical behavior of the embedded damage in the presence of hydrogen, as well as the potential chemical interaction of silicon carbide broken lattice bonds with the hydrogen dissociated from gas by palladium. Implanted samples of silicon carbide were studied using both Raman spectroscopy and FTIR (Fourier Transform-Infrared). The results of this work will be presented during the meeting.
Muntele, I.↗
The Vapor Pressure of Palladium at Temperatures up to 1973K
Understanding high-temperature processes is imperative for modeling the formation of the solar system. It is unfortunate that since the 1950 s little has been done in the area of thermodynamics to continue gaining information on metals such as iron (Fe), nickel (Ni), cobalt (Co), palladium (Pd) and many others. Although the vapor pressures of these metals can be extrapolated to higher temperatures, the data is often limited to temperature ranges too low to be applicable to processes that occur during the formation of the solar system (T approx. 2000K). Experimental techniques inhibited the data in the past by restricting the testing of metals to temperatures below their melting point. Today, higher temperature testing is possible by using a Thermo- Cahn Thermogravimetric system that is able to reach temperatures up to 1973K in vacuo and measure a 10 gram change in a sample with mass of up to 100 grams.
Gardner, K. G.↗
Effects of Palladium Content, Quaternary Alloying, and Thermomechanical Processing on the Behavior of Ni-Ti-Pd Shape Memory Alloys for Actuator Applications
The need for compact, solid-state actuation systems for use in the aerospace, automotive, and other transportation industries is currently driving research in high-temperature shape memory alloys (HTSMA) having transformation temperatures above 100 C. One of the basic high temperature systems under investigation to fill this need is NiTiPd. Prior work on this alloy system has focused on phase transformations and respective temperatures, no-load shape memory behavior (strain recovery), and tensile behavior for selected alloys. In addition, a few tests have been done to determine the effect of boron additions and thermomechanical treatment on the aforementioned properties. The main properties that affect the performance of a solid state actuator, namely work output, transformation strain, and permanent deformation during thermal cycling under load have mainly been neglected. There is also no consistent data representing the mechanical behavior of this alloy system over a broad range of compositions. For this thesis, ternary NiTiPd alloys containing 15 to 46 at.% palladium were processed and the transformation temperatures, basic tensile properties, and work characteristics determined. However, testing reveals that at higher levels of alloying addition, the benefit of increased transformation temperature begins to be offset by lowered work output and permanent deformation or "walking" of the alloy during thermal cycling under load. In response to this dilemma, NiTiPd alloys have been further alloyed with gold, platinum, and hafnium additions to solid solution strengthen the martensite and parent austenite phases in order to improve the thermomechanical behavior of these materials. The tensile properties, work behavior, and dimensional stability during repeated thermal cycling under load for the ternary and quaternary alloys were compared and discussed. In addition, the benefits of more advanced thermomechanical processing or training on the dimensional stability of these alloys during repeated actuation were investigated. Finally, the effect of quaternary alloying on the thermal stability of NiTiPdX alloys is determined via thermal cycling of the materials to increasing temperatures under load. It was found that solid solution additions of platinum and gold resulted in about a 30 C increase in upper use temperature compared to the baseline NiTiPd alloy, providing an added measure of over-temperature protection.
Bigelow, Glen↗
Permeation Rate Equations for Hydrogen and Deuterium in a Palladium-Silver Alloy
Mass transfer of a gas through a selective, solid membrane is an effective method for separation of desired species. This selective permeability is evident in the flow of hydrogen and the isotope deuterium through palladium-silver metal alloy media. In this study, based upon Sieverts’s law and the Arrhenius diffusion equation, an empirical correlation was developed to determine the steady-state permeation rate R, dependence on media temperature T, gas supply pressure p(sub S), and gas backpressure p(sub B) on the lower pressure side. Because of an extensive range of experimental conditions and complete reporting of raw data, the research by Ackerman and Koskinas was used as a source for data allowing empirical equation fitting. Unfortunately, those authors reported best-fit equations that poorly represented their own results. To improve the modeling of the original data and demonstrate the quality of the measurements, the current study develops improved hydrogen and deuterium permeation rate equations: P = 4.22×10(exp −6) A[exp(−704/T)](sq. root p(sub S) − sq. root p(sub B))/t for hydrogen P = 2.12×10(exp −6) A[exp(−468/T )](sq. root p(sub S) − sq. root p(sub B))/t for deuterium for values of cross-sectional area A (sq.cm), medium thickness t (cm), pressure p (psia), and temperature T (Kelvin), giving a permeation rate in mole/minute. These equations model permeation rate data more closely than do several other existing literature sources.
Smith, Phillip J.↗
Transmutations Observed from Pressure Cycling Palladium Silver Metals with Deuterium Gas
Hydrogen, deuterium, and helium gases were separately cycled through a Johnson-Mattheypurifier containing coiled palladium silver alloy tubing: Pd25Ag (75 wt% Pd and 25 wt% Ag).During the cycling of D2 gas, evidence of anomalous heat production was observed. However,during the cycling of H2 and He,very little (H2) or no (He) unusual heat events were observed.After cycling the D2 gas through the coiled tubing for several months, Pd25Ag samples showedan increase in Cu and Fe compared with the amounts in unexposed Pd25Ag. Chromium,manganese, and zinc were detected in gas-cycled Pd25Ag samples, whereas they were notdetected in unexposed Pd25Ag samples. In particular, Zn was present in the gas-cycled Pd25Agmaterial in larger quantities than either Cr or Mn. Although a small amount of Cu was present inthe Pd25Ag coil before the D2 gas cycling, 7 times more was present after the cycling. Multiplematerial characterization techniques were used to obtain both pre-test and post-test elementalcomposition. The results indicate that novel post-test elements, primarily on the surface, werecreated by unknown nuclear mechanisms at low energy.
Gustave C Fralick↗
Σ3(111) Grain Boundaries Accelerate Hydrogen Insertion into Palladium Nanostructures
Grain boundaries (GBs) are frequently implicated as key defect structures facilitating metal hydride formation, yet their specific role remains poorly understood due to their structural complexity. Here, we investigate hydrogen insertion in Pd nanostructures enriched with well-defined Σ3(111) GBs (Pd GB ) synthesized via electrolysis-driven nanoparticle assembly. In situ synchrotron X-ray diffraction reveals that Pd GB exhibits dramatically accelerated hydriding and dehydriding kinetics compared with ligand-free and ligand-capped Pd nanoparticles with similar crystallite sizes. Strain mapping using environmental transmission electron microscopy shows that strain is highly localized at GBs and intensifies upon hydrogen exposure, indicating preferential hydrogen insertion along GB sites. Density functional theory calculations provide mechanistic insight supporting these findings, showing that hydrogen insertion near Σ3(111) GBs is energetically more favorable and that tensile strain lowers insertion barriers. Furthermore, these results provide atomic-level insights into the role of GBs in hydride formation and suggest new design strategies for GB-engineered Pd-based functional materials.
Anions↗
Promoting the oxidative coupling of methanol and dimethylamine using group 1 alkali metals on palladium-gold nanoparticles
PdAu/SiO 2 catalysts were synthesized by strong electrostatic adsorption (SEA) and characterized by TEM, DRIFTS, XRD, XAS, and O 2 -TPD. The use of group 1 alkali salt solutions to control pH during SEA syntheses led to uptake of alkali metals observed reductions in the densities of terminal silanol groups of the SiO 2 support. In the absence of alkali metals, PdAu/SiO 2 catalyzes oxidative C-N bond formation between methanol and dimethylamine (DMA), yielding dimethylformamide (DMF) with ∼95 % carbon selectivity (CO 2 ∼5 %) at temperatures below 413 K. When Na, K, and Cs were present on the catalyst, methyl formate (MF) and tetramethylurea (TMU) were observed as additional products (combined ∼30 % carbon selectivity) while only TMU was detected for the Li-promoted catalyst. Total coupling product rate increased for promoted samples in the order Li < Na < Cs < K, and the apparent kinetics over the Cs-promoted catalyst were distinct from those over the alkali-free catalyst as the apparent reaction order with respect to DMA decreased and the apparent activation energy increased. Finally, this work demonstrates the sensitivity of oxidative coupling reactions to alkali metal promoters and the opportunity to achieve alkali promotion of metal catalysts during SEA synthesis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synergistic Solvent-Surface Interactions Enable Alkyne Semihydrogenation at Palladium
Enabling higher yield and better selectivity for fine-chemical synthesis through heterogeneous catalysis is intricately linked to the interplay of active sites, reaction conditions, and mass transfer influence provided by the catalyst. Alkyne semihydrogenation is ubiquitous in the production of bulk chemicals in the pharmaceutical, polymer, or fine-chemical industries, but product selectivity remains a major challenge. Here, in this study, we demonstrate that the design of catalysts encompassing nickel (Ni) foams as contiguous monolith supports, decorated with ultralow loading of Pd/PdO x nanoparticles on a carbonized polydopamine interface and tuned with a thin layer of Al 2 O 3 , in conjunction with an optimized reaction environment leads to highly selective alkyne semihydrogenation. The reactions demonstrate good functional group tolerance and applicability to flow reactor systems. Combined computational and experimental studies are presented to describe the synergistic effect between the solvent-surface interaction and the degree of Pd surface reduction that are necessary to promote this selectivity. The system highlights the opportunity for catalyst-solvent codesign as a benign alternative to more complex reactants featuring extrinsic poisons or less-favored dopants.
atomic layer deposition↗
Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion
Efficiently removing/converting methane via methane combustion imposes challenges on catalyst design: how to design local structures of a catalytic site so that it has both high intrinsic activity and atomic efficiency? By manipulating the atomic distance of isolated Pd atoms, herein we show that the intrinsic activity of Pd catalysts can be significantly improved for methane combustion via a stable Pd 2 structure on a ceria nanorod support. Guided by theory and confirmed by experiment, we find that the turnover frequency (TOF) of the Pd 2 structure with the Pd–Pd distance of 2.99 Å is higher than that of the Pd 2 structure with the Pd–Pd distance of 2.75 Å; at least 26 times that of ceria supported Pd single atoms and 4 times that of ceria supported PdO nanoparticles. The high intrinsic activity of the 2.99 Å Pd–Pd structure is attributed to the conductive local redox environment from the two O atoms bridging the two Pd 2+ ions, which facilitates both methane adsorption and activation as well as the production of water and carbon dioxide during the methane oxidation process. In conclusion, this work highlights the sensitivity of catalytic behavior on the local structure of active sites and the fine-tuning of the metal–metal distance enabled by a support local environment for guiding the design of efficient catalysts for reactions that highly rely on Pt-group metals.
36 MATERIALS SCIENCE↗