Synthesis, modification, and characterization of CuO/ZnO/ZrO2 mixed metal oxide catalysts for CO2/H2 conversion

Abstract

CuO/ZnO/ZrO2 catalyst systems were synthesized in different ways and comprehensively characterized in order to study synthesis-to-property relations. A series of catalyst samples was prepared by coprecipitation, one-pot synthesis, and wet impregnation. The coprecipitation of multicomponent precipitates is usually a preliminary stage for preparation of mixed oxide catalysts. Cetyltrimethylammonium bromide (CTAB) was used in the surfactant-supported coprecipitation to improve the structural or textural characteristics of the catalytic samples. In the one-pot synthesis, all necessary components are simultaneously converted by evaporation from solutions into solids. During the wet impregnation, zirconium hydroxide is loaded with metal salts. After thermal treatment, all samples formed pure metal oxide forms, which was confirmed by XRD. The specific surface area of the investigated samples and their porous texture were determined by nitrogen adsorption. The reducibility of metal oxides and the kind of CuO phase was characterized by temperature-programmed reduction (TPR), and the surface acid properties by temperature-programmed ammonia desorption (TPAD). The CuO/ZnO/ZrO2 sample with the highest amount of strong acid sites is characterized by the formation of large CuO particles combined with the worst reducibility so that potentially catalytic active Cu/CuO pairs can be formed. One catalyst system was further characterized by in situ diffuse reflection Fourier transform infrared spectroscopy (DRIFTS) to identify surface intermediate species, which may occur during the conversion of CO2/H2 to methanol.