Creation of the active site for methanol synthesis on a Cu/SiO₂ catalyst

Abstract

The effect of ZnO/SiO₂ in a physical mixture of Cu/SiO₂ and ZnO/SiO₂ on methanol synthesis from CO₂ and H₂ was studied to clarify the role of ZnO in Cu/ZnO-based catalysts. An active Cu/SiO₂ was prepared by the following procedure: the Cu/SiO₂ and ZnO/SiO₂ catalysts with a different SiO₂ particle size were mixed and reduced with H₂ at 523-723 K, and the Cu/SiO₂ was then separated from the mixture using a sieve. The methanol synthesis activity of the Cu/SiO₂ catalyst increased with the reduction temperature and was in fairly good agreement with that previously obtained for the physical mixture of Cu/SiO₂ and ZnO/SiO₂. These results indicated that the active site for methanol synthesis was created on the Cu/SiO₂ upon reduction of the physical mixture with H₂. It was also found that ZnO itself had no promotional effect on the methanol synthesis activity except for the role of ZnO to create the active site. The active site created on the Cu/SiO₂ catalyst was found not to promote the formation of formate from CO₂ and H₂ on the Cu surface based on in situ FT-IR measurements. A special formate species unstable at 523 K with an OCO asymmetric peak at ~1585 cm^-1 was considered to be adsorbed on the active site.