Methanol electrooxidation in a 0.5 M sulfuric acid electrolyte containing 1.0 M CH3OH was studied on 30% Pt/carbon and 30% PtRu/carbon (Pt/Ru = 1:1) catalysts using X-ray absorption spectroscopy (XAS). Absorption by Pt and Ru was measured at constant photon energy in the near edge region during linear potential sweeps of 10-50 mV/s between 0.01 and 1.36 V vs rhe. The absorption results were used to follow Pt and Ru oxidation and reduction under transient conditions as well as to monitor Ru dissolution. Both catalysts exhibited higher activity for methanol oxidation at high potential following multiple potential cycles. Correlation of XAS data with the potential sweeps indicates that Pt catalysts lose activity at high potentials due to Pt oxidation. The addition of Ru to Pt accelerates the rate of methanol oxidation at all potentials. Ru is more readily oxidized than Pt, but unlike Pt, its oxidation does not result in a decrease in catalytic activity. PtRu/carbon catalysts underwent significant changes during potential cycling due to Ru loss. Similar current density vs potential results were obtained using the same PtRu/carbon catalyst at the same loading in a membrane electrode assembly half cell with only a Nafion (DuPont) solid electrolyte. The results are interpreted in terms of a bifunctional catalyst mechanism in which Pt surface sites serve to chemisorb and dissociate methanol to protons and carbon monoxide, while Ru surface sites activate water and accelerate the oxidation of the chemisorbed CO intermediate. PtRu/carbon catalysts maintain their activity at very high potentials, which is attributed to the ability of the added Ru to keep Pt present in a reduced state, a necessary requirement for methanol chemisorption and dissociation.
The kinetics of the copper-catalyzed amination of long-chain aliphatic alcohols (octanol and decanol) by monomethylamine and dimethylamine have been investigated in both the gas and liquid phases at temperatures between 440 and 540 K. The individual reactions leading to the production of stable intermediates and products are identified. The rate of dehydrogenation of the alcohol determines the overall rate of alcohol conversion to all products. The rate is first order in alcohol in both the gas and liquid phases and inhibited by alcohol, water, and the reactant amine in the gas phase only. The selectivity is determined primarily by the rate of hydrogenation of an adsorbed Intermediate and the rate of disproportionation of reactant and product amines. The selectivity of the amination reaction to the desired tertiary amine increases with increasing hydrogen pressure, and first increases and then decreases with increasing conversion of alcohol.
Very low surface resistance Tl2Ba2CaCu2O8 films of thickness 1.0 μm on (100) LaAlO3 were fabricated and characterized. The films are highly c-axis oriented (x-ray diffraction rocking curve full width half maximum of 0.68°) with good in-plane epitaxy with respect to the substrate. The Tc of the films was 107.6±0.5 K as measured by ac magnetic susceptibility. The surface resistance at 10 GHz was measured with the parallel plate resonator technique and found to be 23±5 μΩ at 4.2 K, 130±20 μΩ at 77 K, and 300±60 μΩ at 95 K. Using a 20 GHz TE011 end-wall replacement copper cavity, the surface resistance was found to be comparable to that of copper, about 18 mΩ, at 104±1 K. The surface resistance of the films is significantly lower than that of all films reported to date at temperatures above 70 K and only slightly higher than the best high-temperature superconductor films reported to date at 4.2 K.
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