The structure of catalytically active gold on titania

The high catalytic activity of gold clusters on oxides has been attributed to structural effects (including particle thickness and shape and metal oxidation state), as well as to support effects. We have created well-ordered gold mono-layers and bilayers that completely wet (cover) the oxide support, thus eliminating particle shape and direct support effects. High-resolution electron energy loss spectroscopy and carbon monoxide adsorption confirm that the gold atoms are bonded to titanium atoms. Kinetic measurements for the catalytic oxidation of carbon monoxide show that the gold bilayer structure is significantly more active (by more than an order of magnitude) than the monolayer.     

Renewable hydrogen from nonvolatile fuels by reactive flash volatilization

Droplets of nonvolatile fuels such as soy oil and glucose-water solutions can be flash evaporated by catalytic partial oxidation to produce hydrogen in high yields with a total time in the reactor of less than 50 milliseconds. Pyrolysis, coupled with catalytic oxidation of the fuels and their fragments upon impact with a hot rhodium-cerium catalyst surface, avoids the formation of deactivating carbon layers on the catalyst. The catalytic reactions of these products generate approximately 1 megawatt of heat per square meter, which maintains the catalyst surface above 800 degrees C at high drop impact rates. At these temperatures, heavy fuels can be catalytically transformed directly into hydrogen, carbon monoxide, and other small molecules in very short contact times without the formation of carbon.     

Effects of Boundaries on Pattern Formation: Catalytic Oxidation of CO on Platinum

The effect of boundaries on pattern formation was studied for the catalytic oxidation of carbon monoxide on platinum surfaces. Photolithography was used to create microscopic reacting domains on polycrystalline foils and single-crystal platinum (110) surfaces with inert titanium overlayers. Certain domain geometries give rise to patterns that have not been observed on the untreated catalyst and bring to light surface mechanisms that have no analog in homogeneous reaction-diffusion systems.     

Oxidation-resistant gold-55 clusters

Gold nanoparticles ranging in diameter from 1 to 8 nanometers were prepared on top of silicon wafers in order to study the size dependence of their oxidation behavior when exposed to atomic oxygen. X-ray photoelectron spectroscopy showed a maximum oxidation resistance for "magic-number" clusters containing 55 gold atoms. This inertness is not related to electron confinement leading to a size-induced metal-to-insulator transition, but rather seems to be linked to the closed-shell structure of such magic clusters. The result additionally suggests that gold-55 clusters may act as especially effective oxidation catalysts, such as for oxidizing carbon monoxide.     

Powering fuel cells with CO via aqueous polyoxometalates and gold catalysts

Electricity was produced by catalytic oxidation of carbon monoxide (CO) by using gold catalysts at room temperature. The observed rates are faster than conventional processes operating at 500 kelvin or higher for the conversion of CO with water to produce hydrogen and carbon dioxide through the water-gas shift (WGS). By eliminating the WGS reaction, we remove the need to transport and vaporize liquid water in the production of energy for portable applications. This process can use CO-containing gas streams from the catalytic reforming of hydrocarbons to produce an aqueous solution of reduced polyoxometalate compounds that can be used to generate power. The reduced polyoxometalate can be reoxidized in fuel cells that contain simple carbon anodes.     

Atomic-scale structure and catalytic reactivity of the RuO(2)(110) surface

The structure of RuO(2)(110) and the mechanism for catalytic carbon monoxide oxidation on this surface were studied by low-energy electron diffraction, scanning tunneling microscopy, and density-functional calculations. The RuO(2)(110) surface exposes bridging oxygen atoms and ruthenium atoms not capped by oxygen. The latter act as coordinatively unsaturated sites-a hypothesis introduced long ago to account for the catalytic activity of oxide surfaces-onto which carbon monoxide can chemisorb and from where it can react with neighboring lattice-oxygen to carbon dioxide. Under steady-state conditions, the consumed lattice-oxygen is continuously restored by oxygen uptake from the gas phase. The results provide atomic-scale verification of a general mechanism originally proposed by Mars and van Krevelen in 1954 and are likely to be of general relevance for the mechanism of catalytic reactions at oxide surfaces.     

Heterogeneous catalysis: effect of an alternating electric field

Oxidation of carbon monoxide was studcied in a static reactor at 123 degrees +/- 1 degrees C, wtith NiO as catalyst. An alternating electric field of about 22,000 volts per centimeter, peak to peak, was applied normal to the catalytic Surfaces. The rate of oxidation was thereby enhanced by a factor of 6 at 100 cycles per second, with maximum enhancement at between 100 and 200 cycles per second.     

Carbon monoxide balance in nature

Consideration of the steady-state equations for stable carbon monoxide and for radioactive carbon monoxide in the troposphere leads to the conclusion that carbon monoxide is produced at a rate of 5x10(15) grams per year, a value some 25 times greater than the rate of carbon monoxide production from combustion. The concomitant residence time for carbon monoxide is 0.1 year, in agreement with a previous estimate of Weinstock. Hydroxyl radicals are shown to account for both the production of this large amount of carbon monoxide by methane oxidation and for its removal by carbon monoxide oxidation. The average concentration of hydroxyl radicals in the troposphere required to achieve this effect is 2.3x10(6) molecules per cubic centimeter, with a daytime concentration of twice that. Levy and McConnell, McElroy, and Wofsy have deduced concentrations of hydroxyl radicals in the troposphere of the same magnitude from purely photochemical considerations, in support of this model.     

Rare-earth oxides of manganese and cobalt rival platinum for the treatment of carbon monoxide in auto exhaust

The perovskite-like compounds RE(1-X)Pb(5)MnO(3) and RECoO(3), where RE (rare earth) is lanthanum, praseodymium, or neodymium, are active catalysts for the oxidation of carbon monoxide. Crushed single crystals of these compounds compare favorably with commercial platinum catalysts in initial activity and lifetime. Therefore, these compounds are promising substitutes for platinum in devices for the catalytic treatment of auto exhaust.     

Exhaust catalysts: appropriate conditions for comparing platinum and base metal

There are fundamental differences in the behavior of alumina-supported samples of a platinum and a copper-chromium catalyst for oxidation of carbon monoxide in a simulated automotive exhaust stream. Ignoring such differences can result in inappropriate comparisons between oxidation catalysts for automotive application.     

Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters

We demonstrated that platinum (Pt) oxygen-reduction fuel-cell electrocatalysts can be stabilized against dissolution under potential cycling regimes (a continuing problem in vehicle applications) by modifying Pt nanoparticles with gold (Au) clusters. This behavior was observed under the oxidizing conditions of the O2 reduction reaction and potential cycling between 0.6 and 1.1 volts in over 30,000 cycles. There were insignificant changes in the activity and surface area of Au-modified Pt over the course of cycling, in contrast to sizable losses observed with the pure Pt catalyst under the same conditions. In situ x-ray absorption near-edge spectroscopy and voltammetry data suggest that the Au clusters confer stability by raising the Pt oxidation potential.     

Controlling chemical turbulence by global delayed feedback: pattern formation in catalytic CO oxidation on Pt(110)

Control of spatiotemporal chaos is one of the central problems of nonlinear dynamics. We report on suppression of chemical turbulence by global delayed feedback using, as an example, catalytic carbon monoxide oxidation on a platinum (110) single-crystal surface and carbon monoxide partial pressure as the controlled feedback variable. When feedback intensity was increased, spiral-wave turbulence was transformed into new intermittent chaotic regimes with cascades of reproducing and annihilating local structures on the background of uniform oscillations. The global feedback further led to the development of cluster patterns and standing waves and to the stabilization of uniform oscillations. These findings are reproduced by theoretical simulations.     

Soil as a sink for atmospheric carbon monoxide

The rate of carbon monoxide oxidation by soil increased with increasing carbon monoxide concentration in the gas phase, in line with Michaelis-Menten kinetics. Rates of carbon monoxide oxidation were determined for 20 soils at 0 degrees , 10 degrees , 20 degrees , and 30 degrees C. The observed oxidation rates were used to calculate a global soil uptake rate of atmospheric carbon monoxide of 4.1 x 10(14) grams per year, which is slightly less than the amount of carbon monoxide believed to be produced annually as a result of fossil fuel combustion.     

Enhanced bonding of gold nanoparticles on oxidized TiO2(110)

We studied the nucleation of gold clusters on TiO2(110) surfaces in three different oxidation states by high-resolution scanning tunneling microscopy. The three TiO2(110) supports chosen were (i) reduced (having bridging oxygen vacancies), (ii) hydrated (having bridging hydroxyl groups), and (iii) oxidized (having oxygen adatoms). At room temperature, gold nanoclusters nucleate homogeneously on the terraces of the reduced and oxidized supports, whereas on the hydrated TiO2(110) surface, clusters form preferentially at the step edges. From interplay with density functional theory calculations, we identified two different gold-TiO2(110) adhesion mechanisms for the reduced and oxidized supports. The adhesion of gold clusters is strongest on the oxidized support, and the implications of this finding for catalytic applications are discussed.     

Palladium: preparation and catalytic properties of particles of uniform size

A method has been developed for the preparation of uniform palladium particles of diameter from 55 to 450 angstroms. Uniform particles of gold layered on palladium were also synthesized. Hydrothermal treatment of aluminum hydroxide sol was used to prepare rods of alumina with uniform cross section from 100 to 500 angstroms and of varying lengths. The palladium was adsorbed as individual particles on alumina rods, both present in aqueous suspension. Then the suspension was dried to give a catalyst containing metal particles of uniform size dispersed in open pores produced by the intermeshing of the alumina rods. This procedure guaranteed the absence of diffusion control in the rate of reactions observed experimentally. All stages of the preparation were monitored with the electron microscope. The kinetics of the ethylene-hydrogen reaction were examined by means of a pulse technique. The number of active sites determined by carbon monoxide titration of the surface was equal to the number of surface atoms as determined by the calculation of the quantities of compounds involved in the synthesis and electron microscope examination. Furthermore, the activity per site depended on the method of preparation, being four times smaller when sodium formate was used as a reducing agent instead of sodium citrate. This may be due to the fact that the shape of particles makes certain crystallographic planes more favorable. Decrease in the size of particles to 56 angstroms produced no effect on catalytic activity beyond that due to the increase in the number of surface atoms. The activity of commercial 5 percent palladium on alumina diluted 100-fold with alumina gave 80.4 percent conversion with propylene and 82.7 percent conversion with ethylene. Thus there was little difference in the behavior of the two olefins.     

Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.     

Visualizing gas molecules interacting with supported nanoparticulate catalysts at reaction conditions

Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.     

Hydrogen Cyanide Production During Reduction of Nitric Oxide over Platinum Catalysts: Transient Effects

The formation of hydrogen cyanide during the catalytic reduction of nitric oxide (NO) with carbon monoxide and hydrogen was studied with a bench-scale flow reactor. The previously reported inhibition by sulfur dioxide of the formation of hydrogen cyanide was found to be counteracted by transient admission of oxygen to the catalyst. These results are discussed in the context of the control of automotive emissions of NO and the prevention of hydrogen cyanide production during such control.     

Carbon monoxide in rainwater

Concentrations of carbon monoxide in rainwater collected at widely diverse locations show up to a 200-fold supersaturation relative to the partial pressure of the gas in the atmosphere. These results indicate the existence of an additional natural source of carbon monoxide not heretofore considered. Production of carbon monoxide in clouds is tentatively attributed to the photochemical oxidation of organic matter or the slight dissociation of carbon dioxide induced by electrical discharges, or both. Methane concentrations measured in the same rainwater show that the partitioning of this gas, unlike that of carbon monoxide, is very close to a state of equilibrium.