Copper-nickel alloy films hydrogenation

Copper-nickel alloy films similarly deposited at high substrate temperatures and annealed in either hydrogen or deuterium were used to study the hydrogenation of buta-1,3-diene (119) and the exchange of cyclopentane with deuterium (120). Rates of buta-1,3-diene hydrogenation as a function of alloy composition resemble the pattern for butene-1 hy-... 

Gharpurey, M.K. and Emmett, P.H. "Study of the hydrogenation of ethylene over homogenized copper-nickel alloy films." /. Phys. Chem. 65 1182-1184 1961. 

The catalytic effect of copper-nickel alloys as a function of composition for the reaction 2H H2 is shown in Fig. 6.17 [53]. Above 60 at.% Cu, the filled d-band is less favorable to hydrogen adsorption hence, favorable collisions of gaseous H with adsorbed H are less probable, and the reaction rate decreases. The similarity to passive behavior of copper-nickel alloys, which also decreases above 60 at.% Cu, can be noted. The parallel conditions affecting passivity and catalytic activity support the viewpoint that the passive films on transition metals and their alloys are chemisorbed. 

The temperature behavior of the alloy catalysts in the heterogeneous recombination of hydrogen atoms was different for rich in nickel alloys from one side and for rich in copper from the other. For the three alloy catalyst films, i.e. Ni97Cu3, Ni77Cu23, and Ni57Cu43 (numbers represent... 

This conclusion was additionally confirmed by Palczewska and Janko (67) in separate experiments, where under the same conditions nickel-copper alloy films rich in nickel (and nickel films as well) were transformed into their respective hydride phases, which were proved by X-ray diffraction. The additional argument in favor of the transformation of the metal film into hydride in the side-arm of the Smith-Linnett apparatus consists of the observed increase of the roughness factor ( 70%) of the film and the decrease of its crystallite size ( 30%) after coming back from low to high temperatures for desorbing hydrogen. The effect is quite similar to that observed by Scholten and Konvalinka (9) for their palladium catalyst samples undergoing the (a — j8) -phase transformation. 

In order that the possibility of contamination of catalysts with traces of oxides could be eliminated Campbell and Emmett (51) studied the catalytic activity of metallic films of nickel and its alloys with copper or gold. They were deposited under a high vacuum and then sintered (alloys also homogenized) in hydrogen at 5 cm Hg pressure at 350°C or 500°C. The films were subsequently allowed to cool to room temperature and only... 

In studies on the para-hydrogen conversion rate on nickel and its alloys with copper other authors also noted the poisoning effect of the sorbed hydrogen. Singleton (53) mentioned the poisoning of nickel film catalysts by the slow-sorbed hydrogen. Shallcross and Russell (54) observed a similar phenomenon for nickel and its alloys with copper at — 196°C. At higher... 

Takeuchi et al. prepared films by the evaporation of copper and nickel metals or their alloys on a substrate cooled by liquid oxygen. Prior to use, the film was treated in vacuum at 30 or 250°C. The catalytic activity was tested by the hydrogenation reaction of ethylene. Their result is illustrated in Fig. 8. Essentially similar results have been reported by Volter and Alsdorf... 

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