Surface and catalytic properties of the CuO/Al2O3 system as influenced by doping with CeO2 or ZrO2 and by γ-irradiation

The effects of doping the CuO/Al2O3 system with CeO2 or ZrO2, or alternatively treatment with gamma-irradiation, on its surface and catalytic properties were investigated using nitrogen adsorption at -196degreesC, the decomposition of H2O2 at 20-40degreesC and the oxidation of CO by O-2 at 175degreesC. The pure solids were prepared by wet impregnation with copper nitrate dissolved in the least amount of distilled water of finely powdered solid Al(OH)(3) precalcined at 400degreesC, followed by drying the resulting product and subjecting the same to calcination at 500degreesC. The doped solids were prepared by treating Al(OH)(3) precalcined at 400degreesC with a known amount of dopant, i.e. cerium or zirconyl nitrate dissolved in the least amount of distilled water, prior to impregnation with the copper nitrate solution. The amount of copper oxide thus introduced was fixed at 13.5 wt% while the amounts of dopants were varied between 1 wt% and 10 wt% CeO2 or ZrO2. The results obtained indicated that ZrO2 doping increased the degree of dispersion of the CuO phase, while CeO2 treatment had the reverse effect. Doping the CuO/Al2O3 system with CeO2 or ZrO2 led to an increase of 15.4% or 8.1%, respectively, in its BET surface area. The catalytic activity of the system towards the decomposition of H2O2 decreased on doping with ZrO2 but increased when CeO2 was used as a dopant. gamma-Irradiation (at 20-160 Mrad) of CuO/Al2O3 solids resulted in a measurable and progressive decrease in their catalytic activity towards H2O2 decomposition. In CO oxidation with O-2, ZrO2 treatment of the CuO/Al2O3 solids brought about a progressive increase in their catalytic activity with the maximum value (a 31% increase) being observed in the presence of 3 wt% ZrO2 but then decreasing with further increases in the amount of dopant present until the final value attained with 10 wt% ZrO2 was smaller than that measured for the pure CuO/Al2O3 catalyst sample. In contrast, the addition of the smallest amount of CeO2 (1 wt%) led to an effective increase of 69% in the catalytic activity of the CuO/Al2O3 system towards the O-2 oxidation of CO, which then decreased when further amounts of CeO2 were added to the system although still exhibiting a catalytic activity greater than that of the undoped catalyst sample. Doping or gamma-irradiation of the CuO/Al2O3 system had no influence on the activation energy for the decomposition of H2O2 in the presence of the resulting solid catalysts although the concentrations of catalytically active sites present on the surfaces of the solids investigated were modified by such treatment.