Insight into the Nature of the ZnO_x Promoter during Methanol Synthesis

Despite the great commercial relevance of zinc-promoted copper catalysts for methanol synthesis, the nature of the Cu-ZnO_xsynergy and the nature of the active Zn-based promoter species under industrially relevant conditions are still a topic of vivid debate. Detailed characterization of the chemical speciation of any promoter under high-pressure working conditions is challenging but specifically hampered by the large fraction of Zn spectator species bound to the oxidic catalyst support. We present the use of weakly interacting graphitic carbon supports as a tool to study the active speciation of the Zn promoter phase that is in close contact with the Cu nanoparticles using time-resolved X-ray absorption spectroscopy under working conditions. Without an oxidic support, much fewer Zn species need to be added for maximum catalyst activity. A 5-15 min exposure to 1 bar H₂at 543 K only slightly reduces the Zn(II), but exposure for several hours to 20 bar H₂/CO and/or H₂/CO/CO₂leads to an average Zn oxidation number of +(0.5-0.6), only slightly increasing to +0.8 in a 20 bar H₂/CO₂feed. This means that most of the added Zn is in a zerovalent oxidation state during methanol synthesis conditions. The Zn average coordination number is 8, showing that this phase is not at the surface but surrounded by other metal atoms (whether Zn or Cu), and indicating that the Zn diffuses into the Cu nanoparticles under reaction conditions. The time scale of this process corresponds to that of the generally observed activation period for these catalysts. These results reveal the speciation of the relevant Zn promoter species under methanol synthesis conditions and, more generally, present the use of weakly interacting graphitic supports as an important strategy to avoid excessive spectator species, thereby allowing us to study the nature of relevant promoter species.