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At least 19 records

Strong metal-support interactions

It has been demonstrated that synergistic metal-support effects can occur which markedly enhance specific activity and alter selectivity in certain reactions. Because of the presence of such effects in certain reactions conducted under reducing conditions (that is, under H2 pressure), but not others, the creation of unique sites at the metal-support interface seems to be the best model at the present time to explain this behavior. The postulation of these sites, which are specific for a certain reactant such as CO, provides an effective explanation for the higher methanation rates that have been reported over some catalysts. The creation of these sites in the adlineation zone is facilitated by hydrogen spillover from the metal surface, and this same process can also enhance the reduction of many oxide supports. Although oxygen spillover is much less probable due to its higher heat of adsorption, it is much less well understood and the possibility of rate enhancements in CO oxidation caused by special interface sites cannot be discounted at the present time. Consequently, this seems to be an important area of future research.

Vannice, M. Albert↗

UHV studies of the interaction of CO with small supported metal particles, Pd/mica

The interaction of carbon monoxide with small palladium particles supported on UHV-cleaved and heat-treated single-crystal mica was studied. The Pd particles were characterized and tested using the techniques of flash thermal desorption, Auger electron spectroscopy, core electron energy loss spectroscopy, and transmission electron microscopy. Evidence is presented for CO decomposition on Pd particles during CO adsorption-desorption experiments. The rate of CO decomposition increased rapidly with diminishing particle size. Residual carbon from CO decomposition blocked CO adsorption and had a strong poisoning effect on the CO oxidation reaction.

Doering, D. L.↗

UHV studies of the interaction of CO with small supported metal particles, Ni/mica

The interaction of carbon monoxide with small nickel (Ni) particles supported on UHV-cleaved mica was studied using flash thermal desorption, Auger electron spectroscopy, and transmission electron microscopy. Molecular desorption was accompanied by decomposition of CO at a rate strongly dependent on particle size. Recombination of surface-precipitated carbon with adsorbed oxygen was observed, and gas-induced morphological particle changes because of exposure to CO and O2 are analyzed in some detail.

Doering, D. L.↗

Surface studies with (clean) supported metal particles and clusters

Small particles are ideal for combined studies with surface analytical and electron microscopy/diffraction methods. In this way crystallography, microstructure, morphology, physical stability, and electronic structure can be correlated directly with chemical reactivity. Various integrated experimental approaches for conducting model studies with UHV-evaporated particles have been successfully developed; they entail the use of TPD, AES, XPS, and work function measurements on one hand and standard TEM/TED, in-situ TEM/TED, and in-situ STED/TEM techniques on the other hand. The essential features of four particular experimental approaches are discussed and a selection of representative results is presented to illustrate the potential usefulness of such studies in the field of catalysis.

Poppa, H. R.↗

Metal-support interactions during the adsorption of CO on thin layers and islands of epitaxial palladium

Islands and continuous layers of palladium were grown in an ultrahigh vacuum on substrates of Mo(110)c(14 x 7)-O, designated MoO(x), and of clean Mo(110). It was found that as-deposited islands and layers exhibited bulk palladium adsorption properties for CO when deposited at room temperature and for palladium thicknesses in excess of about 3 monolayers. CO adsorption was drastically reduced, however, on annealing. For islands, annealing temperatures of as low as 400 K led to some reduction in CO adsorption whereas more severe reductions were found to occur at 600 K for islands and at 800 K for continuous multilayers. The deactivation depended on the palladium thickness, the substrate species and the extent of thermal treatments. Auger electron spectroscopy, temperature-programmed desorption and Delta-Phi measurements were combined to interpret the deactivation behavior in terms of substrate-support interactions involving the diffusion of substrate species towards the palladium surface.

Park, C.↗

CO oxidation studies over supported noble metal catalysts and single crystals: A review

The catalytic oxidation of CO over noble metal catalysts is reviewed. Results obtained on supported noble metal catalysts and single crystals both at high pressures and under UHV conditions are compared. The underlying causes which result in surface instabilities and multiple steady-state oscillations are considered, in particular, the occurrence of hot spots. CO islands of reactivity, surface oxide formation and phase transformations under oscillatory conditions are discussed.

Boecker, Dirk↗

Model studies in catalysis with uhv-deposited metal particles and clusters

Small supported metal particles have become a popular area of intense research interest, and important contributions to the considered problems are being made from the fields of uhv technology, thin film physics surface science, and surface and thin film instrumentation. Attention is given to insulating supports, particulate metal deposits and their properties, metal/support interactions and gas exposures, and integrated experimental approaches. It is concluded that major contributions to the field of model catalysis should be forthcoming in the near future from uhv-based methods of research. Catalysis and catalysis-related problem areas expected to benefit from advanced model studies include catalyst preparation processing, sintering mechanisms for metals and alloys, separation of initial and final state effects for supported clusters, and the influence of particle and/or support morphologies.

Poppa, H.↗

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.↗

Low conducting metal screen support flange

In a very high or very low temperature duct system in which duct insulation is terminated at selected locations so as to be not coextensive with the duct, an annular metal perforated or mesh screen support flange is used, as a low conductor of heat or cold, between the duct and an outer insulation cover to retain the end of the insulation and to support its usually very thin cover. The screen may be Z-shaped in cross section having a small diameter annular portion to surround and be secured to the duct adjacent the end of the insulation. A generally radially extending portion of the screen extends outwardly from the small diameter portion and adjacent the end of the insulation. The periphery of the radially extending portion is in alignment with the outer peripheral surface of the insulation and the outer peripheral surface of the insulation cover. A large diameter annular portion of the screen extends longitudinally from the periphery in the direction opposite the small diameter portion, and is adapted to surround the insulation and its cover and be secured thereto. The screen may also be U or channel-shaped with one longitudinally directed leg secured to the insulation cover and the other leg secured to the duct under the insulation.

Lestak, Robert G.↗

Steam reforming of n-hexane on pellet and monolithic catalyst beds. A comparative study on improvements due to heat transfer

Monolithic catalysts with higher available active surface areas and better thermal conductivity than conventional pellets beds, making possible the steam reforming of fuels heavier than naphtha, were examined. Performance comparisons were made between conventional pellet beds and honeycomb monolith catalysts using n-hexane as the fuel. Metal-supported monoliths were examined. These offer higher structural stability and higher thermal conductivity than ceramic supports. Data from two metal monoliths of different nickel catalyst loadings were compared to pellets under the same operating conditions. Improved heat transfer and better conversion efficiencies were obtained with the monolith having higher catalyst loading. Surface-gas interaction was observed throughout the length of the monoliths.

Source record↗

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

Klettlinger, Jennifer Lindsey Suder↗

Mounting for diodes provides efficient heat sink

Efficient heat sink is provided by soldering diodes to metal support bars which are brazed to a ceramic base. Electrical connections between diodes on adjacent bars are made flexible by metal strips which aid in heat dissipation.

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Bonding Elastomers To Metal Substrates

Improved, economical method for bonding elastomers to metals prevents failures caused by debonding. In new technique, vulcanization and curing occur simultaneously in specially designed mold that acts as form for desired shape of elastomer and as container that positions and supports metal parts. Increases interface adhesion between metal, adhesive, and elastomer.

Dickerson, George E.↗

Investigation of NOx Removal from Small Engine Exhaust

Contribution of emissions from small engines to the air pollution is significant. Due to differences in operating conditions and economics, the pollution control systems designed for automobiles will be neither suitable nor economically feasible for use on small engines. The objective of this project was to find a catalyst for the removal of NOx from the exhaust of small engines which use a rich air to fuel ratio. The desired catalyst should be inexpensive so that the cost of the pollution control unit will be only a small fraction of the total equipment cost. The high cost of noble metals makes them too expensive for use as NOx catalyst for small engines. Catalytic reduction of Nitrogen Oxide (NO) can also be accomplished by base-metal oxide catalysts. The main disadvantage of base-metal catalysts is their deactivation by poisons and high temperatures. Requirements for the length of the life of the small engine exhaust catalysts are much less than those for automobile exhaust catalysts. Since there is no oxygen in the exhaust gases, reduction selectivity is not a problem. Also, the reducing exhaust gases might help prevent the harmful interactions of the catalyst with the support. For these reasons only the supported metal oxide catalysts were investigated in this project.

Akyurtlu, Ates↗

Investigation of NO(x) Removal from Small Engine Exhaust

Contribution of emissions from small engines to the air pollution is significant. Due to differences in operating conditions and economics, the pollution control systems designed for automobiles will be neither suitable nor economically feasible for use on small engines. The objective of this project was to find a catalyst for the removal of NOx from the exhaust of small engines which use a rich air to fuel ratio. The desired catalyst should be inexpensive so that the cost of the pollution control unit will be only a small fraction of the total equipment cost. The high cost of noble metals makes them too expensive for use as NOx catalyst for small engines. Catalytic reduction of NO can also be accomplished by base-metal oxide catalysts. The main disadvantage of base-metal catalysts is their deactivation by poisons and high temperatures. Requirements for the length of the life of the small engine exhaust catalysts are much less than those for automobile exhaust catalysts. Since there is no oxygen in the exhaust gases, reduction selectivity is not a problem. Also, the reducing exhaust gases might help prevent the harmful interactions of the catalyst with the support. For these reasons only the supported metal oxide catalysts were investigated in this project.

Akyurtlu, Ates↗

Design Analysis and Thermo-Mechanical Fatigue of a Polyimide Composite for Combustion Chamber Support

Polyimide composites are being evaluated for use in lightweight support structures designed to preserve the ideal flow geometry within thin shell combustion chambers of future space launch propulsion systems. Principles of lightweight design and innovative manufacturing techniques have yielded a sandwich structure with an outer face sheet of carbon fiber polyimide matrix composite. While the continuous carbon fiber enables laminated skin of high specific stiffness; the polyimide matrix materials ensure that the rigidity and durability is maintained at operation temperatures of 316 C. Significant weight savings over all metal support structures are expected. The protypical structure is the result of ongoing collaboration, between Boeing and NASA-GRC seeking to introduce polyimide composites to the harsh environmental and loads familiar to space launch propulsion systems. Design trade analyses were carried out using relevant closed form solutions, approximations for sandwich beams/panels and finite element analysis. Analyses confirm the significant thermal stresses exist when combining materials whose coefficients of thermal expansion (CTEs) differ by a factor of about 10 for materials such as a polymer composite and metallic structures. The ramifications on design and manufacturing alternatives are reviewed and discussed. Due to stringent durability and safety requirements, serious consideration is being given to the synergistic effects of temperature and mechanical loads. The candidate structure operates at 316 C, about 80% of the glass transition temperature T(sub g). Earlier thermomechanical fatigue (TMF) investigations of chopped fiber polyimide composites made this near to T(sub g), showed that cyclic temperature and stress promoted excessive creep damage and strain accumulation. Here it is important to verify that such response is limited in continuous fiber laminates.

Thesken, J. C.↗