Evolution of Cu-Zn-Si oxide catalysts in the course of reduction and reoxidation as studied by in situ X-ray diffraction analysis, transmission electron microscopy, and magnetic susceptibility methods

Abstract

The reduced and reoxidized Cu-Zn-Si oxide catalysts as layered copper-zinc hydroxo silicates with the zincsilite structure were studied using in situ and ex situ X-ray diffraction analysis, transmission electron microscopy, and the temperature dependence of magnetic susceptibility. The catalysts were prepared by homogeneous deposition-precipitation. It was found that Cu0 particles were formed on the surface of a layered hydrosilicate with the zincsilite structure upon reduction with hydrogen. The reoxidation of the reduced samples with a mixture of oxygen and an inert gas, which contained no more than 0.05 vol % O2, resulted in the formation of individual Cu2O and CuO phases; copper ions did not return to the hydrosilicate structure. Catalytic tests of Cu-Zn-Si catalysts in methanol synthesis indicate that the specific catalytic activity of copper metal particles grows linearly with increasing zinc loading. This fact suggests that copper metal particles, which were obtained by the reduction of Cu2+ ions from the copper-zinc hydroxo silicate with the zincsilite structure, were responsible for activity in methanol synthesis. Consequently, the ability to return copper ions to a precursor compound in reoxidation with oxygen at low concentrations, which is known for reduced Cu/ZnO catalysts (these catalysts are highly active in methanol synthesis), is not related to the catalytic activity in methanol synthesis.