Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts

Abstract

The promoting effect of Al, Ga, and Mg on the support in Cu/ZnO catalysts for methanol synthesis has been investigated. Different unpromoted and promoted ZnO supports were synthesized and impregnated with Cu metal in a subsequent step. All materials, supports, and calcined and activated catalysts were characterized by various methods, including contactless (microwave) conductivity measurements under different gas atmospheres. Small amounts of promoters were found to exhibit a significant influence on the properties of the oxide support, concerning textural as well as electronic properties. We found correlations between the conductivity of the ZnO support and the activity of the catalyst in the reverse water-gas shift reaction (rWGS) as well as in methanol synthesis. In rWGS the activation energy and reaction order in H2 are decreased upon promotion of the ZnO support with the trivalent promoters Al3+ and Ga3+, indicating an electronic promotion. In methanol synthesis, results point to a structural promotion by Al3+ and Ga3+. A detrimental effect of Mg2+ doping was observed in both reactions. This effect is discussed in the context of the reducibility of ZnO under reaction conditions, which can be tuned by the promoter in different ways. The reducibility is seen as a critical property for the dynamic metal support interaction of the Cu/ZnO system.