Catalysis by amorphous metal alloys. Part 1.—Hydrogenation of olefins over amorphous Ni–P and Ni–B alloys

Abstract

Amorphous Ni–P (Ni81P19) and Ni–B (Ni62B38) alloys have been prepared by the rapid quenching method. The untreated alloys are inactive for the hydrogenation of olefins, but successive pretreatments of the alloys with the dilute HNO3, oxygen and hydrogen bring about greater catalytic activity than that possessed by the crystalline alloys. Measurements of the ESCA spectra of the surfaces of the alloys have indicated that the alloys become active by the partial oxidation of the nickel and phosphorus or boron on the surface. Buta-1,3-diene is hydrogenated to give isomeric butenes of constant composition, and butenes isomerise rapidly to give a similar composition to that obtained on the hydrogenation of buta-1,3-diene. The hydrogenation of buta-1,3-diene is first and zeroth order with respect to the partial pressures of hydrogen and buta-1,3-diene, respectively. These results are explained by assuming that the hydrogen and the olefins are not competing for adsorption on the same sites and that hydrogen is activated on electron-deficient nickel atoms formed by electron transfer from nickel to the oxidised species.