Manganese Oxide as a Promoter for Copper Catalysts in CO₂ and CO Hydrogenation

In this work, we discuss the role of manganese oxide as a promoter in Cu catalysts supported on graphitic carbon during hydrogenation of CO₂ and CO. MnO_x is a selectivity modifier in an H₂/CO₂ feed and is a highly effective activity promoter in an H₂/CO feed. Interestingly, the presence of MnO_x suppresses the methanol formation from CO₂ (TOF of 0.7 ⋅ 10^-3 s^-1 at 533 K and 40 bar) and enhances the low-temperature reverse water-gas shift reaction (TOF of 5.7 ⋅ 10^-3 s^-1) with a selectivity to CO of 87 %_C. Using time-resolved XAS at high temperatures and pressures, we find significant absorption of CO₂ to the MnO, which is reversed if CO₂ is removed from the feed. This work reveals fundamental differences in the promoting effect of MnO_x and ZnO_x and contributes to a better understanding of the role of reducible oxide promoters in Cu-based hydrogenation catalysts.