Oxidative Fluorination of Cu/ZnO Methanol Catalysts

The influence of a mild difluorine treatment on Cu/ZnO precatalysts for methanol synthesis was investigated. It led to the incorporation of 1.2EL1.3±0.1 wt % fluoride into the material. Fluorination considerably increased the amount of ZnOx related defect sites on the catalysts and significantly increased the space‐time yields. Although the apparent activation energy EA,app for methanol formation from CO2 and H2 was almost unchanged, the EA,app for the reverse water‐gas shift (rWGS) reaction increased considerably. Overall, fluorination led to a significant gain in methanol selectivity and productivity. Apparently, also the quantity of active sites increased.